JPH07225445A - Surface latent image type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having high contrast after desensitization and a sharp toe of its characteristic curve. CONSTITUTION:This silver halide photographic sensitive material has at least one surface latent image type silver halide emulsion layer on the base and surface latent image type silver halide particles in the emulsion layer contain tyanochromium complex ions represented by the formula [Cr(CN)6-nLn]<m-> [where L is H2O or OH, (n) is 0 or 1 and (m) is 3 or 4].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a surface latent image type silver halide photographic light-sensitive material. In particular, the invention is
The present invention relates to a surface latent image type silver halide photographic light-sensitive material having a high contrast and a sharp foot.

[0002]

2. Description of the Related Art High sensitivity, fine graininess and low fog are required for the basic performance of silver halide photographic light-sensitive materials. One of the means for satisfying them is a metal doping technique. The metal doping technique is carried out for the purpose of modifying the physical properties of silver halide grains and increasing the efficiency (quantum sensitivity) of converting photoelectrons into latent images that are active for development.
Specifically, the metal doping technique is a technique for incorporating (doping) metal ions alone or a metal complex containing a ligand into silver halide grains. The metal doping modifies the properties of the silver halide grains and can improve the performance of the emulsion as a whole. A general and practical surface latent image type silver halide photographic emulsion is desired to have even higher contrast. In particular, the light-sensitive material for graphic arts is desired to have a high contrast even if the sensitivity is lowered. The hard contrast means that the gradient of the gradation portion (straight portion) of the characteristic curve in which the horizontal axis represents the exposure amount and the vertical axis represents the optical density has a large inclination. Regarding the gradation, it is also important that the foot of the characteristic curve (the area of the exposure amount where the optical density starts to increase) is cut off (the rising edge is sharp). Similarly, in a silver halide photographic light-sensitive material such as color photographic paper, the part corresponding to the low density part of the characteristic curve is in high contrast, that is, the foot part is cut off, and a clear image is obtained. Desirable to get.

Research Disclosure
Ch Disclosure), 17643, section IA, for metal doping techniques, describes metal ions or metal complexes that can be introduced during grain formation. In the early days of metal doping technology, typical examples of metal complexes used are shown in US Pat. No. 2,448,060.
It is a metal complex of platinum, palladium, iridium, rhodium and ruthenium. When doped with these water-soluble metal complexes, they function as antifoggants and stabilizers. Particularly, a hexacoordinated metal complex of palladium (IV value) also exhibits a sensitizing effect. The complex described in this document has a halide such as chloride or bromide as a ligand. U.S. Pat. No. 3,690,888 discloses a process for making silver halide containing polyvalent metal ions. The manufacturing method includes the step of forming silver halide grains in the presence of a protective colloid mainly composed of an acrylic polymer. Examples of polyvalent metal ions used include bismuth, iridium, lead and osmium ions. In addition to metal ions, the complexes described in this document have a halide such as chloride or bromide as a ligand. The above references disclose the effects obtained by incorporating metal ions into the silver halide grains.

Regarding the dopant containing cyanide ion, Japanese Patent Publication No. 48-35373 discloses yellow blood salt and red blood salt which are hexacyano metal complexes of iron as the dopant containing cyanide ion. The effect of this invention is
Regardless of the type of ligand, only when the complex contains iron ions. U.S. Pat. No. 3,790,390 is
A silver halide emulsion containing a cyano complex of iron (II), iron (III) and cobalt (III) and containing a spectral sensitizing dye is disclosed. U.S. Pat. No. 4,847,191 discloses silver halide grains formed in the presence of a rhodium (III) complex having 3, 4, 5 or 6 cyano ligands. This reference reports a reduction in high illumination failure for silver halide emulsions containing these grains. The above documents also disclose the effect of incorporating metal ions into the silver halide grains.

Japanese Unexamined Patent Publication Nos. 2-20853 and 2-20
No. 854 each discloses silver halide grains formed in the presence of a rhenium, ruthenium, osmium or iridium complex having 4 or more cyano ligands. These documents describe, as effects of emulsions containing these grains, improvement of sensitivity and gradation stability with time, and improvement of low illumination failure. JP-A-2-20852 and 2-208
55, No. 3-118535 and No. 3-11853.
No. 6, each of which discloses a cyanide ion and a bridging ligand (eg, N
O, NS, CO, and (O) ₂ ) are used in combination. In these references, a hexacoordinated metal complex consisting of a metal ion and 6 ligands is doped by replacing 7 silver vacancies of 1 silver ion and 6 adjacent halide ions inside the crystal. A new concept of being done is being proposed.

Japanese Unexamined Patent Publication No. 6-51423 (European Patent No. 0
573066A1) discloses an invention in which an internal latent image type direct positive silver halide emulsion is doped with a hexacyano metal complex. The metals in the complex include chromium, manganese, cobalt, iridium, ruthenium, rhodium,
Rhenium and osmium are listed. The effect of the present invention is to obtain an internal latent image type direct positive silver halide emulsion having high contrast and high sensitivity. The internal latent image type direct positive silver halide emulsion is a silver halide emulsion which forms a latent image mainly inside the silver halide upon image exposure. The special properties of this emulsion can be used to directly form a positive image. In specific image formation, after an internal latent image is formed by imagewise exposure, when developing with a surface developer (a developer that does not selectively develop silver halide grains having an internal latent image), uniform exposure or Carry out a nucleating agent treatment. Due to these complicated processes, the internal latent image type direct positive silver halide emulsion has relatively low sensitivity (compared with the surface latent image type silver halide emulsion described below). For this reason,
In improving internal latent image type direct positive silver halide emulsions, high sensitivity is always required.

On the other hand, a normal silver halide emulsion is of a surface latent image type and forms a latent image mainly on the surface of the silver halide upon imagewise exposure. In image formation using a surface latent image type silver halide emulsion, after a surface latent image is formed by imagewise exposure, a developing solution is used to selectively develop silver halide grains having a surface latent image. The surface latent image type silver halide emulsion has relatively high sensitivity. Therefore, depending on the application, even if the sensitivity is reduced, other properties are improved (for example,
It may be desired to make the gradation harder. Such a contrast enhancement effect (desensitization contrast) accompanied by a decrease in sensitivity is similar to the effect of the invention described in JP-A-6-51423.
It is distinguished from the contrast enhancement effect which is not accompanied by the decrease in sensitivity.

As described above, the mechanism of image formation is fundamentally different between the internal latent image type emulsion and the surface latent image type emulsion. Therefore, the effect of the above metal doping may be significantly different between the internal latent image type emulsion and the surface latent image type emulsion. As described above, the metal doping technique is performed for the purpose of changing the efficiency (quantum sensitivity) of converting photoelectrons into a latent image that is active for development. Therefore, the effect of metal doping greatly changes depending on whether the target latent image exists inside the particle or on the surface of the particle.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a surface latent image type silver halide light-sensitive material having a desensitized high-contrast tone and a sharp foot of the characteristic curve.

[0010]

The present invention is a surface latent image type silver halide photographic light-sensitive material having at least one surface latent image type silver halide emulsion layer on a support, wherein the surface of the emulsion layer is Provided is a surface latent image type silver halide photographic light-sensitive material, wherein the latent image type silver halide grain contains a cyanochrome complex ion represented by the following formula (I). (I) [Cr (CN) _6-n L _n ] ^m -wherein L is H ₂ O or OH, n is 0 or 1, and m is 3 or 4.

The surface latent image type silver halide photographic light-sensitive material of the present invention can be implemented in the following modes (2) to (11). (2) The surface latent image type silver halide grains contain the cyanochrome complex ions in an amount of 1 × 10 ⁻⁸ per mol of silver halide.
The surface latent image type silver halide photographic light-sensitive material as described in (1), wherein the surface latent image type silver halide photographic light-sensitive material is contained in the range of 1 × 10 ^-2 mol. (3) The surface latent image type silver halide photographic light-sensitive material according to (1), wherein the surface latent image type silver halide grain has a halogen composition such that the silver chloride content is 50 mol% or more. (4) The surface latent image type silver halide photographic light-sensitive material according to (3), wherein the surface latent image type silver halide grain has a halogen composition such that the silver chloride content is 80 mol% or more.

(5) The surface latent image type silver halide photographic light-sensitive material according to (1), wherein the surface latent image type silver halide emulsion layer further contains a mercapto heterocyclic compound. (6) The surface latent image type silver halide emulsion layer further contains a mercapto heterocyclic compound in an amount of 1 per mol of silver halide.
The surface latent image type silver halide photographic light-sensitive material according to (5), which is contained in the range of ^{x10 -5 to} 5 x 10 ^-2 mol. (7) The surface latent image type silver halide photographic light-sensitive material according to (1), wherein the surface latent image type silver halide emulsion layer further contains a tetraazaindene compound. (8) The surface latent image type silver halide emulsion layer further contains a tetraazaindene compound in an amount of 1 per mol of silver halide.
The surface latent image type silver halide photographic light-sensitive material according to (7), which is contained in the range of ^{x10 -5 to} 3 x 10 ^-1 mol.

(9) The surface latent image type silver halide photographic light-sensitive material according to (1), wherein the surface latent image type silver halide grain further contains a complex ion of iron, ruthenium, osmium, cobalt, rhodium or iridium. . (10) The surface latent image type silver halide photographic light-sensitive material according to (1), which has a coating pH value in the range of 4.0 to 6.5. (11) The surface latent image type silver halide photographic light-sensitive material according to (10), which has a coating pH value in the range of 5.0 to 6.5.

[0014]

According to the study of the present inventors, when the surface latent image type silver halide grains are doped with cyanochrome complex ions,
It was found that an image with remarkably high contrast was obtained although the sensitivity was remarkably lowered. In particular, the foot break of the characteristic curve is significantly improved. As described above, in a general and practical surface latent image type silver halide photographic emulsion, it may be desired that the tone is high even if the sensitivity is lowered. Particularly in photographic papers and photosensitive materials for graphic arts, image quality including gradation is prioritized over sensitivity. The surface latent image type silver halide light-sensitive material of the present invention can be very advantageously applied to such applications where image quality is prioritized.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The silver halide emulsion used in the silver halide light-sensitive material of the present invention is of the surface latent image type. The surface latent image type emulsion is a silver halide emulsion which forms a latent image mainly on the surface of silver halide grains upon imagewise exposure. The surface latent image type emulsion can be specifically judged as follows. Two kinds of samples are prepared by coating a certain amount of silver halide emulsion on a transparent support. 0.01 to 1 for these
Give the exposure at a fixed time of second. One sample is developed in the following surface developing solution at 20 ° C. for 5 minutes.
The rest of the samples were 5 ° C in the following internal developer at 20 ° C.
Develop for minutes. The case where the maximum density of the surface-developed sample is higher than the maximum density of the internally-developed sample is defined as a surface latent image type silver halide emulsion. This maximum concentration is
It is measured by an ordinary photographic density measuring method.

──────────────────────────────────── Surface developer ──────── ───────────────────────────── N-methyl-p-aminophenol sulfite 2.5g 1-Ascorbic acid 10g Potassium metanitrate 35g Odor Potassium iodide 1 g Water added 1 liter ─────────────────────────────────────

──────────────────────────────────── Internal developer ───────── ──────────────────────────── N-Methyl-p-aminophenol sulfite 2g Sodium nitrite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (Monohydrate) 52.5 g Potassium bromide 5 g Potassium iodide 0.5 g Water added 1 liter ─────────────────────────── ──────────

In the present invention, the surface latent image type silver halide grains as described above are doped with cyanochrome complex ions.
The cyanochrome complex ion is represented by the following formula (I). (I) [Cr (CN) _6-n L _n ] ^m -wherein L is H ₂ O or OH, n is 0 or 1, and m is 3 or 4. n is preferably 0. m is preferably 3.

The cyanochrome complex ion exists in an ionic form in an aqueous solution. Therefore, the counter cation of the complex ion is not so important technically. As the counter cation, an ion which is easily miscible with water and suitable for the precipitation operation of the silver halide emulsion may be selected. Examples of counter cations include alkali metal ions (eg sodium ions,
Potassium ion, rubidium ion, cesium ion,
Lithium ion), ammonium ion and alkylammonium ion. The alkyl ammonium ion is shown in the following formula (II).

(II) [R ¹ R ² R ³ R ⁴ N] ^{+ In the} formula, each of R ¹ , R ² , R ³ and R ⁴ is a lower alkyl group having 6 or less carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, iso-propyl and n-butyl. R ¹ , R ² , R ³ and R
It is preferred that ⁴ are the same. Examples of preferred alkylammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n-butyl) ammonium ion.

The cyanochrome complex ion can be used by dissolving it in water or a mixed solvent of water and an organic solvent. Examples of suitable water-miscible organic solvents include alcohols, ethers, glycols, ketones, esters and amides. The solution of cyanochrome complex ions can be added directly to the reaction solution at the time of silver halide grain formation. Further, grain formation may be carried out by adding it to an aqueous halide solution for forming silver halide grains or a solution other than that.

When silver halide grains are doped with cyanochrome complex ions, they can be uniformly present inside the grains. Further, the particle surface layer may be doped with a high concentration of cyanochrome complex ions. Further, silver halide fine particles doped with cyanochrome complex ions may be used to physically ripen the silver halide grains and introduce the cyanochrome complex ions into the grain surface phase. The above methods can be combined and implemented. A method for doping high-concentration cyanometal complex ions with a particle surface layer is disclosed in JP-A 2-1.
No. 25245, No. 3-188437 and No. 4-20.
It is described in each gazette of No. 8936. The method using silver halide fine particles doped with a cyano metal complex ion is described in US Pat. Nos. 5,252,451 and 5,256,530. In the case of the cyanochrome complex ion of the present invention, the same method can be used. As a general rule, it is preferable that the cyanochrome complex ions are uniformly present inside the silver halide grains. However, minute crystal nuclei in the initial stage of particle formation (particle diameter: about 0.04 to 0.2 μm)
If a cyanochrome complex ion is added at the stage of forming, the crystal shape of the particles may become unstable. Therefore, it is preferable to add the cyanochrome complex ion after the formation of the fine crystal nuclei is completed. It is preferable that the cyanochrome complex ions are uniformly present in the silver halide grain portion other than the fine crystal nuclei.

The amount of cyanochrome complex ions doped is preferably in the range of 1 × 10 ^{-8 to} 1 × 10 ^-2 mol, and more preferably in the range of 1 × 10 ^{-7 to} 1 × 10 ^-3 mol, per mol of silver halide. Is more preferable, and the range of 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol is most preferable. The hydrogen ion concentration in the reaction solution when the cyanochrome complex ion is added is preferably pH 3 or higher.

The doping amount and doping rate of the metal complex in the silver halide grain can be measured by quantifying the central metal (chromium in the case of the present invention) of the doped metal complex. Atomic absorption method, ICP method (In
Inductively Coupled Plasma Spectrometry: Inductively coupled high frequency plasma spectroscopy or ICPMS method
ctively Coupled Plasma Mass Spectrometry) can be adopted.

Examples of the cyanochrome complex ion are given below. (I-1) [Cr ( CN) 6] 3- (I-2) [Cr (CN) 5 (H 2 O)] 3- (I-3) [Cr (CN) 5 (OH)] 4-

The fact that the cyanochromium complex exhibits a photographic effect different from that of other cyanometal complexes can be estimated as follows. When light is absorbed by silver halide grains, photoelectrons and holes are generated. The lifetime of the excited photoelectrons can be measured using the microwave photoconductivity method. For example,
VIs such as iron, ruthenium, cobalt and iridium
Emulsion doped with Group II hexacyano metal complex (JP-A-6-
In Japanese Patent No. 51423), the photoelectron lifetime is extended and a temporary shallow electron trap is generated. As is well known, the generation of electron traps increases the probability that particles will contribute to latent image formation and improves photographic sensitivity.

On the other hand, even with the same cyano metal complex, in the case of the cyanochrome complex of the present invention, when the lifetime of excited electrons is measured similarly, it shows a remarkably short lifetime. Therefore, it is considered that the cyanochrome complex has a strong electron trapping ability. It is presumed that this is the cause of lowering the photographic sensitivity and increasing the contrast. As described above, the photographic effect of the cyanochrome complex has a clear difference from the effect of the Group VIII hexacyano metal complex in terms of the physical properties of the doped particles.

The surface latent image type silver halide emulsion layer preferably contains a mercapto heterocyclic compound. A preferable mercapto heterocyclic compound is represented by the following formula (III).

[0029]

[Chemical 1]

In the formula, Q represents an atomic group necessary for forming a 5-membered or 6-membered heterocycle, and M is a cation.
An aromatic ring (eg, a benzene ring) may be condensed with the heterocycle.

Examples of the heterocyclic ring formed by Q are an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, Includes naphthoselenazole ring and benzoxazole ring. Examples of the cation represented by M include a hydrogen ion, an alkali metal (eg, sodium, potassium) ion, and an ammonium ion. Particularly preferred mercapto heterocyclic compounds are represented by the following formulas (III-1), (III-2), (III-3) and (III-
It is represented by 4).

[0032]

[Chemical 2]

In the formula, R ¹¹ is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, and Z is —NH— or —O. -Or-S-, and M is a cation.

[0034]

[Chemical 3]

In the formula, R ¹² is an aryl group or a cycloalkyl group, and M is a cation. The aryl group and the cycloalkyl group may have a substituent. Examples of the aryl group and the cycloalkyl group are shown by the following formulas.

[0036]

[Chemical 4]

In the formula, R ¹³ , R ¹⁴ and R ¹⁵ are each an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an amide group, a carbamoyl group or a sulfonamide group. And n is 0, 1 or 2.

R ¹¹ and R in the formulas (III-1) and (III-2)
Examples of alkyl groups at ¹³ , R ¹⁴ and R ¹⁵ include methyl, ethyl and butyl. Examples of alkoxy groups include methoxy and ethoxy. Examples of the carboxyl or sulfo salt include sodium salt and ammonium salt.

In R ¹¹ of the formula (III-1), examples of the aryl group include phenyl and naphthyl. Examples of halogen atoms include chlorine and bromine. Formula (III-
In R ¹³ , R ¹⁴ and R ¹⁵ of 2), examples of the amide group include acetamide and benzamide. Examples of the carbamoyl group include ethylcarbamoyl and phenylcarbamoyl. Examples of sulfonamide groups include methanesulfonamide and benzenesulfonamide. The alkyl group, alkoxy group, aryl group, amino group, amide group, carbamoyl group and sulfonamide group may further have a substituent. For example, an amino group substituted with an alkylcarbamoyl group, that is, an alkyl-substituted ureido group is also included in the substituted amino group.

[0040]

[Chemical 5]

In the formula, Z is —NR ¹⁶ —, an oxygen atom or a sulfur atom. R ¹⁷ is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, —SR ¹⁸ , or —
NR ¹⁹ R ²⁰ , -NHCOR ²¹ , -NHSO ₂ R ²² or a heterocyclic group. R ¹⁶ and R ¹⁸ are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
It is an aryl group, -COR ²³ or -SO ₂ R ²⁴ . R
¹⁹ and R ²⁰ are each a hydrogen atom, an alkyl group or an aryl group. R ²¹ , R ²² , R ²³ and R ²⁴ are
Each is an alkyl group or an aryl group. M is a cation.

R ¹⁶ , R ¹⁷ , R ¹⁸ , R ^{19 of} the formula (III-3),
Examples of alkyl groups for R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ include methyl, benzyl, ethyl and propyl. Examples of aryl groups include phenyl and naphthyl. R ¹⁶ , R ¹⁷ and R ^{18 of} formula (III-3)
In, an example of an alkenyl group is propenyl. An example of a cycloalkyl group is cyclohexyl. Formula (III-
In R ¹⁷ of 3), examples of the heterocyclic group include furyl and pyridinyl. The alkyl group, aryl group, alkenyl group, cycloalkyl group and heterocyclic group may further have a substituent. For example, an alkyl group substituted with an aryl group, that is, an aralkyl group is also included in the substituted alkyl group.

[0043]

[Chemical 6]

In the formula, R ²⁵ is R ¹⁷ in the formula (III-3).
Has the same definition as M is a cation. R ²⁶ and B ²⁷ have the same definitions as R ¹⁶ and R ¹⁹ in formula (III-3), respectively. Specific examples of the compound represented by the formula (III) are shown below.

[0045]

[Chemical 7]

[0046]

[Chemical 8]

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13]

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

[0069]

[Chemical 31]

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

[0073]

[Chemical 35]

[0074]

[Chemical 36]

[0075]

[Chemical 37]

[0076]

[Chemical 38]

The addition amount of the mercaptoheterocyclic compound is preferably 1 × 10 ^{−5 to} 5 × 10 ⁻² mol per mol of silver halide, and 1 × per mol of silver halide.
More preferably, it is 10 ⁻⁴ to 1 × 10 ⁻² mol.
Regarding the addition method to the surface latent image type silver halide emulsion layer,
There is no particular limitation. It may be added during the formation of silver halide grains, during physical ripening, during chemical ripening, or during preparation of the coating solution.

The surface latent image type silver halide emulsion layer preferably contains a tetraazaindene compound. Preferred tetraazaindene compounds are represented by the following formulas (IV) and (V)
It is represented by.

[0079]

[Chemical Formula 39]

[0080]

[Chemical 40]

In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ and R
⁴² , R ⁴³ and R ⁴⁴ are each a hydrogen atom, an alkyl group, an aryl group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group, a halogen atom,
It represents a cyano group, a carboxyl group, an alkoxycarbonyl group or a heterocyclic group. R ³¹ and R ³² , R ³² and R ³³ , R ⁴¹
And R ⁴² or R ⁴² and R ⁴³ may combine to form a 5- or 6-membered ring. However, at least one of R ³¹ and R ³³ represents a hydroxy group. Similarly, at least one of R ⁴¹ and R ⁴³ represents a hydroxy group.

The above alkyl group may be cyclic or branched. The alkyl group preferably has 1 to 20 carbon atoms. The alkoxy group preferably has 1 to 20 carbon atoms. The alkylthio group preferably has 1 to 6 carbon atoms. The alkoxycarbonyl group preferably has 2 to 20 carbon atoms. The heterocyclic group preferably has a 5- or 6-membered ring. Examples of the heteroatom of the heterocyclic group may include a nitrogen atom, an oxygen atom and a sulfur atom. The alkyl group, aryl group, amino group and carbamoyl group may further have a substituent. Examples of the substituent include an aliphatic group and an aromatic group. The tetraazaindene compound may form a polymer. The repeating unit of such a polymer is represented by the following formula (VI).

[0083]

[Chemical 41]

In the formula, R ⁵¹ is a hydrogen atom or an alkyl group, X is a monovalent group obtained by removing one hydrogen atom from the compound represented by the formula (IV) or (V), and J is a divalent group. It is a valent linking group. X is the above formula (IV) or (V)
One hydrogen atom may be removed from the part of R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ or R ^{44 in} the above.

Examples of alkyl groups in formulas (IV), (V) and (VI) include methyl, ethyl, n-propyl, is
o-propyl, n-butyl, iso-butyl, tert-butyl,
Hexyl, cyclohexyl, cyclopentylmethyl, octyl, dodecyl, tridecyl, heptadecyl are included. Examples of the substituent of the alkyl group include an aryl group, a heterocyclic group, a halogen atom, a carboxy group, an alkoxycarbonyl group (preferably having 2 to 6 carbon atoms), an alkoxy group (preferably having 19 or less carbon atoms). And hydroxy groups are included. Examples of substituted alkyl groups are benzyl, phenethyl, chloromethyl, 2-chloroethyl, trifluoromethyl, carboxymethyl, 2-carboxyethyl, 2- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2-methoxyethyl, hydroxymethyl. And 2-hydroxyethyl.

Examples of aryl groups include phenyl and naphthyl. Examples of the substituent of the aryl group include an alkyl group (preferably having 4 or less carbon atoms), a halogen atom, a carboxy group, a cyano group, an alkoxycarbonyl group (preferably having 6 or less carbon atoms), a hydroxy group and an alkoxy. A group (preferably having 6 or less carbon atoms) is included. Examples of the substituted aryl group include p-tolyl, m-tolyl, p-chlorophenyl, p-bromophenyl, o-.
Included are chlorophenyl, m-cyanophenyl, p-carboxyphenyl, o-carboxyphenyl, o- (methoxycarbonyl) phenyl, p-hydroxyphenyl, p-methoxyphenyl and m-ethoxyphenyl. Examples of the substituent of the amino group include an alkyl group (eg, methyl, ethyl, butyl), an acyl group (eg, acetyl, propionyl, benzoyl) and a sulfonyl group (eg, methanesulfonyl). Examples of substituted amino groups include dimethylamino, diethylamino, butylamino and acetamide.

Examples of alkoxy groups include methoxy, ethoxy, butoxy and heptadecyloxy. Examples of the alkylthio group include methylthio, ethylthio and hexylthio. Examples of the substituent of the carbamoyl group include an alkyl group (preferably having 20 or less carbon atoms).
And aryl groups (preferably phenyl or naphthyl). Examples of the substituted carbamoyl group include methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl and phenylcarbamoyl. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Heterocyclic groups may form two or three condensed rings. Examples of heterocyclic groups are furyl, pyridyl, 2- (3-methyl) benzothiazolyl and 1-
Benzotriazolyl is included. In the substituted alkyl group for R ³⁴ or R ⁴⁴ , when the substituent is a heterocyclic group,
Substituents represented by the following formula (VII) are preferred.

[0088]

[Chemical 42]

In the formula, R ⁶¹ , R ⁶² and R ⁶³ are each represented by the formula (IV)
Has the same definition as R ³¹ , R ³² and R ^{33 in} .
n is 2, 3 or 4. Next, specific examples of the compound represented by any of the formulas (IV), (V) and (VI) are shown.

[0090]

[Chemical 43]

[0091]

[Chemical 44]

[0092]

[Chemical formula 45]

[0093]

[Chemical formula 46]

[0094]

[Chemical 47]

[0095]

[Chemical 48]

[0096]

[Chemical 49]

[0097]

[Chemical 50]

[0098]

[Chemical 51]

[0099]

[Chemical 52]

[0100]

[Chemical 53]

[0101]

[Chemical 54]

[0102]

[Chemical 55]

[0103]

[Chemical 56]

[0104]

[Chemical 57]

[0105]

[Chemical 58]

[0106]

[Chemical 59]

[0107]

[Chemical 60]

[0108]

[Chemical formula 61]

[0109]

[Chemical formula 62]

[0110]

[Chemical formula 63]

[0111]

[Chemical 64]

[0112]

[Chemical 65]

The addition amount of the tetraazaindene compound is preferably 1 × 10 ^{−5 to} 3 × 10 ⁻¹ mol, and preferably 3 × 10 ^{−4 to} 1 × 10 ⁻¹ mol, per mol of silver halide. Is more preferable. The addition amount varies depending on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the surface latent image type emulsion layer and other layers, and the type of the antifoggant compound. Therefore, it is desirable to experimentally select the optimum amount. By adding the tetraazaindene compound to the silver halide emulsion,
The compound can be easily incorporated into the silver halide emulsion layer. When the compound is contained in the non-photosensitive hydrophilic colloid layer, the compound may be similarly added to the coating liquid for the non-photosensitive layer. The compound is preferably added in the form of a solution. Water and an organic solvent are used as the solvent of the solution. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols (eg, methanol, ethanol), esters (eg, ethyl acetate) and ketones (eg, acetone). The tetraazaindene compound may be well dissolved in an alkaline aqueous solution.
In that case, it is convenient to use an alkaline aqueous solution. When the tetraazaindene compound is added to the silver halide emulsion, it can be added at any time from the step of forming silver halide grains to the step of coating the silver halide emulsion. It is preferable to start after the chemical ripening step, and more preferably to add after the chemical ripening step and before coating.

When the silver halide grains are doped with a cyanochrome complex ion, the tone is high and the effect of cutting the legs is obtained by itself. Addition of a mercaptoheterocyclic compound or a tetraazaindene compound thereto further improves the storage stability over time and the maximum optical density. With respect to the compounds of the mercapto heterocyclic compound and the tetraazaindene compound, a sufficient effect can be obtained even if one of the compounds is used.
You may use together two or more types of compounds about each. Further, the mercapto heterocyclic compound and the tetraazaindene compound may be used in combination.

The silver halide grains have a silver chloride content of 50.
It is preferable to have a halogen composition such that it is at least mol%. The silver chloride content is more preferably 80 mol% or more, and most preferably 90 mol% or more. In the present invention, silver chloride, silver chlorobromide or silver chloroiodobromide grains having a silver chloride content of 50 mol% or more can be used. In particular, silver halide grains made of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. When grains containing substantially no silver iodide are used,
The development processing time can be shortened. The term "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. A halogen composition in which 0.01 to 3 mol% of silver iodide is introduced on the surface of the high silver chloride grains may be adopted. Such a halogen composition can be employed for the purpose of enhancing high illuminance sensitivity, enhancing spectral sensitization sensitivity, or enhancing temporal stability of a light-sensitive material (JP-A-3-84545). The halogen composition of the emulsion may differ between grains. By using an emulsion having the same halogen composition among grains, it is easy to homogenize the properties of each grain.

Regarding the halogen composition distribution inside the silver halide emulsion grains, there are grains having a uniform structure and grains having a non-uniform structure. The silver halide grains having a uniform structure have the same composition in any part of the grain. The grains having a non-uniform structure include grains having a laminated structure in which a halogen portion has a different halogen composition between a core portion inside a silver halide grain and a shell portion surrounding the same (including a constitution of a plurality of layers). Other non-uniformly structured particles have a non-layered portion with a different halogen composition inside or on the surface of the particle (on the surface of the particle, different edge portions, corners, or surfaces are bonded with different composition portions)
Are included. In order to obtain high sensitivity, particles of any heterogeneous structure are advantageously used rather than particles of uniform structure. Particles having a non-uniform structure are also preferable from the viewpoint of pressure resistance. When the silver halide grains have a non-uniform structure, the boundary between different halogen compositions may be an unclear boundary forming a mixed crystal due to the difference in composition. Further, a continuous structural change may be positively introduced at the boundary.

The high silver chloride emulsion preferably has a structure having a localized silver bromide phase inside or on the surface of a silver halide grain in the form of a layer or a layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of 10 mol% or more, more preferably more than 20 mol%. The silver bromide content of the silver bromide localized phase can be analyzed using an X-ray diffraction method (for example, described in “New Experimental Chemistry Course 6 Structural Analysis” (Maruzen) edited by the Chemical Society of Japan).
The localized phase can be introduced inside the particles, on the edges, corners or faces of the particle surface. It is particularly preferable that the localized phase grows epitaxially on the corners of the grains.
It is also effective to increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In this case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of silver halide grains is
It is preferably in the range of 0.1 to 2 μm. The average particle size means the number average of the diameters of circles equivalent to the projected areas of individual particles as the particle size. The particle size distribution is preferably monodisperse. In particular,
The coefficient of variation (= standard deviation of particle size distribution / average particle size) is preferably 20% or less, more preferably 15% or less, and most preferably 10% or less. For the purpose of obtaining a wide latitude, a plurality of monodisperse emulsions may be mixed and used in the same layer. For the same purpose, a plurality of monodisperse emulsions may be coated in multiple layers. The shape of the silver halide grains has a regular crystal form such as a cube, a tetradecahedron or an octahedron, or an irregular crystal form such as a sphere or a plate. , And those having a composite form thereof. The emulsion may have a structure in which emulsions having various crystal forms are mixed. In the present invention, the content of the particles having the above-mentioned regular crystal form is preferably 50% or more, more preferably 70% or more, and 90% or more.
% Or more is most preferable. The silver halide emulsions may contain tabular grains in greater than 50 percent of total grain projected area. The tabular grains generally have an aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more.

For the purpose of preparing a monodisperse silver halide emulsion, a silver halide solvent can be used. Examples of the silver halide solvent include thiocyanates, thioether compounds, thioureas, thione compounds, amine compounds, rhodancali and rhodammone. Thiocyanates, thioether compounds and thioureas are preferred. Also,
Ammonia can also be used in combination as long as it does not adversely affect. For thiocyanates, see US Pat.
No. 64, No. 2448534, and No. 3320069. Regarding thioether compounds, US Pat. Nos. 3,271,157 and 3,574,628,
No. 3704130, No. 4276347 and No. 42.
No. 97439 is described in each specification. Regarding thione compounds, JP-A Nos. 53-82408 and 53-1443.
19 and 55-77737.
The amine compound is described in JP-A No. 54-100717.

The silver halide emulsion can be produced by a known method. In general, a silver salt aqueous solution and a halide aqueous solution are added to a reaction vessel having a gelatin aqueous solution with efficient stirring. For the specific method, see P. Glafkides, “Shimmy
Chimie et Phys
ique Photographeque) "(Paul Montel
tel), 1967), G.F.Duffin (G.
F. Duffin), "Photofraffic emulsion.
Chemistry (Photographic Emulsion Chemistry) "
(Published by Focal Press, 1966) and by VL Zelikman, “Making and Coating Photographic Emulsion”.
(Published by Focal Press, 1964). Any of the acidic method, the neutral method and the ammonia method can be adopted. As the method for reacting the soluble silver salt and the soluble halide, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase where silver halide is produced, that is, a controlled double jet method can be used. Further, as described in British Patent No. 1535016 and Japanese Patent Publication Nos. 48-36890 and 52-16364, the addition rate of silver nitrate or an aqueous solution of alkali halide is changed according to the grain formation rate. Good. As described in U.S. Pat. No. 4,242,445 and Japanese Patent Laid-Open No. 55-158124, it is preferable to grow rapidly within a range not exceeding the critical supersaturation rate by using a method of changing the concentration of the aqueous solution. According to these methods, re-nucleation does not occur and silver halide grains grow uniformly.

At the time of forming silver halide grains, the above-mentioned silver halide solvent can be used for controlling grain growth. In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, thallium salt, iron salt or its complex, ruthenium salt or its complex salt, osmium salt or its complex salt, cobalt salt or its complex salt, rhodium salt or its complex salt , Iridium salt or complex salt thereof may coexist. You may form what is called a double structure particle | grain which consists of an inside (core part) and an outside (shell part) of a particle. Furthermore, triple structure particles and multilayer structure particles of more than that (described in JP-A-60-22284).
May be formed. In order to introduce the structure into the emulsion grains, not only the wrapping structure as described above but also a so-called junction structure can be formed. Regarding the particles having a junction structure, JP-A-58-10852.
No. 6, No. 59-16254, No. 59-133540 and Japanese Patent Publication No. 58-24772, and European Patent 199,290A2.

The crystal to be bonded has a composition different from that of the host crystal. The bonded crystal is generated by bonding to the edge or corner of the host crystal, or the face. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition. In the case of a junction structure, in addition to the combination of silver halides, a silver salt compound not having a rock salt structure such as rhodan silver and silver carbonate may be combined with silver halide to form a junction structure. Also,
A non-silver salt compound such as PbO may also have a junction structure. In the grains of silver iodobromide grains having the core-shell type structure, the core portion can have a structure having a high silver iodide content. On the contrary, it is also possible that the shell portion has a high silver iodide content. Similarly, for a grain having a junction structure, a grain structure in which the host crystal has a high silver iodide content and a junction crystal in which the silver iodide content is relatively low, and vice versa are possible. Boundary portions having different halogen compositions of grains having these structures may form a mixed crystal due to a difference in composition and may be an unclear boundary.
Also, continuous structural changes may be positively introduced.

Silver halide emulsions are processed to give roundness to grains (EP 96727B1 and EP 64412).
B1 each description) may be implemented. The emulsion may be subjected to surface modification treatment (described in German Patent No. 2306447C2 and JP-A No. 60-221320). Dislocation lines may be introduced into the silver halide grains. Silver halide grains having dislocation lines are disclosed in US Pat.
No. 06461.

Gelatin is advantageously used as a binder or protective colloid in the emulsion layer or intermediate layer of the light-sensitive material.
Hydrophilic polymers other than gelatin may also be used. Examples of other hydrophilic polymers include proteins (eg, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein), sugar derivatives (eg, cellulose derivatives, sodium alginate, starch derivatives) and synthetic hydrophilic polymers. Polymer (eg, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole,
These copolymers) can be mentioned. Examples of the above cellulose derivative include hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate ester. As the gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used. Enzyme-processed gelatin is described in Bulletin of Japan Photographic Society (Bull. Soc. Photo. Japan), 16
Vol. 30, 30 (1966). A hydrolyzate of gelatin can also be used.

An inorganic or organic hardener may be added to the hydrophilic colloid layer constituting the photographic layer or the back layer. Hardeners include chromium salts, aldehyde salts, N-
Methylol compounds, active halogen compounds, active vinyl compounds, N-carbamoylpyridinium salts and haloamidinium salts can be used. Active halogen compounds, active vinyl compounds, N-carbamoylpyridinium salts and haloamidinium salts are preferred because of their fast curing speed. Active halogen compounds and active vinyl compounds are
It is more preferable because it provides more stable photographic characteristics.
Examples of aldehydes that make up the aldehyde salt include formaldehyde, glyoxal and glutaraldehyde. An example of the N-methylol compound is dimethylol urea. Examples of active halogen compounds include 2,4-
Included are dichloro-6-hydroxy-1,3,5-triazine and its sodium salt. Examples of active vinyl compounds are 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide).
Included are vinyl polymers having ethane, bis (vinylsulfonylmethyl) ether and vinylsulfone groups in the side chains. Examples of N-carbamoylpyridinium salts are:
(1-morpholinocarbonyl-3-pyridinio) methanesulfonate. Examples of haloamidinium salts are 1
-(1-chloro-1-pyridinimethylene) pyrrolidinium-2 naphthalene sulfonate.

The silver halide emulsion is generally spectrally sensitized. As the spectral sensitizing dye, methine dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye and hemioxonol dye can be used. Cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. Spectral sensitizing dyes such as cyanine dyes generally have a basic heterocycle.
Examples of the hetero ring include a pyrroline ring, an oxazoline ring, a thiazoline ring, a pyrrole ring, an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a tetrazole ring and a pyridine ring. An aliphatic ring or an aromatic ring may be condensed with these rings. Examples of the condensed ring include indolenine ring, benzindolenine ring, indole ring,
It includes a benzoxadol ring, a naphthoxazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a benzimidazole ring and a quinoline ring. These rings may have a substituent on a carbon atom. The ring of the merocyanine dye or the complex merocyanine dye is a 5-membered or 6-membered heterocycle having a ketomethylene structure. Examples of the ring having a ketomethylene structure include pyrazolin-5-one ring, thiohydantoin ring, 2-thiooxazolidine-2,4-dione ring, thiazolidine-
It includes the 2,4-dione ring, the rhodanine ring and the thiobarbituric acid ring.

Two or more kinds of sensitizing dyes may be used in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. A supersensitizer may be used together with the sensitizing dye. The supersensitizer is a dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light. Examples of supersensitizers include aminostilbenzene compounds substituted with a nitrogen-containing heterocyclic group (US Pat. No. 2,933,339).
No. 0 and No. 3635721), a condensate of an aromatic organic acid and formaldehyde (US Pat. No. 3743)
No. 510), a cadmium salt, and an azaindene compound. Regarding combinations of sensitizing dyes, U.S. Pat. Nos. 3,615,613 and 3,615,641,
No. 3,617,295 and No. 3,635,721 are described.

The halogenated emulsion is generally chemically sensitized.
The chemical sensitization is performed by sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization, reduction sensitization, or a combination thereof. In sulfur sensitization, an unstable sulfur compound that can react with silver ions to form silver sulfide is used as a sulfur sensitizer. Regarding sulfur sensitization, P. Glafkides, "Chimie e
"T Physique Photographeque" (published by Paul Montel, 1
987, 5th edition), Research Teclosure, 3
No. 07105, edited by TH James, "The Theory of the
Photographic Process "(Macmillan, 1977
4th edition), and H. Frieser, "Die Grundlagen.
der Photographischen Prozess mit Silver-halogenide
n "(Akademische Verlagsgeselbshaft, 1968)
There is a description in. Examples of sulfur sensitizers include thiosulfates (eg,
Sodium thiosulfate, p-toluenethiosulfonate, thioureas (eg, allylthiourea, N, N′-diphenylthiourea, triethylthiourea, acetylthiourea, N-ethyl-N ′-(4-methyl-) 2-thiazolyl) thiourea), thioamides (eg, thioacetamide, N-phenylthioacetamide), rhodanines (eg, rhodanine, N-ethyl rhodanine, 5-benzylidene rhodanine, 5-benzylidene-N-ethyl-). Rhodanine, diethyl rhodamine), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides, polysulfides, thiosulfonic acids,
Includes mercapto compounds (eg, cysteine), polythionates, elemental sulfur and sodium sulfide. Generally, thiosulfates, thioureas, thioamides and rhodanines are used.

In selenium sensitization, an unstable selenium compound is used as a selenium sensitizer. Regarding selenium sensitization, Japanese Examined Patent Publication Nos. 43-13489 and 44-15748.
JP-A-4-25832, 4-40324, 4-109240, 4-147250 and 4-.
-271341 is described in each publication. And the like. Examples of selenium sensitizers include selenoureas (eg, selenourea, N, N-dimethylselenourea, N, N-diethylselenourea, tetramethylselenourea, N, N, N′-trimethyl-N ′). -Acetylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-chlorophenylcarbonylselenourea, N, N, N'- Trimethyl-N'-4-nitrophenylcarbonyl selenourea), selenoamides (eg,
Selenoacetamide, N, N-dimethylselenobenzamide), selenoketones (eg, selenoacetone, selenoacetophenone, bis- (adamantyl) selenoketone), isoselenocyanates (eg, allyl isoselenocyanate), selenocarboxylic acids and their esters. (Eg, selenopropionic acid, methyl-3-selenobutyrate), selenides (eg, dimethyl selenide, diethyl selenide, triphenylphosphine selenide), selenophosphates (eg, tri-p-tolylseleno) Phosphate) and colloidal metal selenium.

Regarding tellurium sensitization, US Pat.
499, 3320069, 3772031,
British Patent Nos. 235211, 1121496, 12
95462, 1396696 and Canadian Patent 8
No. 00958 each specification, Journal of Chemicals
Society Chemical Communication (J.Ch
em.Soc., Chem.Commun.), 635 (1980), 11
02 (1979), 645 (1979), Journal of Chemical Society Parkinson Transaction (J.Chem.Soc., Perkin.Trans.) 1, 2
191 (1980), JP-A-4-204640 and JP-A-4-333043. Examples of tellurium sensitizers include colloidal tellurium, telluroureas (eg, allyl tellurourea, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ′, N ′).
-Dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isostere cyanates (eg, allyl isotellocyanate), telluroketones (eg, telluroacetone,
Telluroacetophenone), telluroamides (eg, telluroacetamide, N, N-dimethyltelurobenzamide), tellurohydrazide (eg, N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg,
t-butyl-t-hexyl telluroester), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), negative Gelatins containing charged telluride ions (described in GB 1295462), potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt and allyl tellurocyanate are included.

In noble metal sensitization, noble metal compounds such as gold, platinum, palladium and iridium are used as noble metal sensitizers. For precious metal sensitization, see P. Grafkide
s, "Chimie et Physique Photographique" (Paul
Montel, 1987, 5th edition) and research
T. Closure, No. 307105. Gold sensitization is particularly preferable. Examples of gold sensitizers include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide. Gold sensitizers include U.S. Pat. Nos. 2,642,361 and 5,049,484;
No. 5,049,485 is described in each specification.

In reduction sensitization, a reducing compound is used as a reduction sensitizer. For reduction sensitization, see P. Grafkide
s, "Chimie et Physique Photographique" (Paul
Montel, 1987, 5th edition) and research
T. Closure, 307, 307105. Examples of reduction sensitizers include aminoiminomethanesulfinic acid (= thiourea dioxide), borane compounds (eg, dimethylamineborane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine), polyamine compounds (eg,
Diethylenetriamine, triethylenetetramine), stannous chloride, silane compounds, reductones (eg ascorbic acid), sulfites, aldehyde compounds and hydrogen gas are included.

Two or more kinds of chemical sensitization may be combined and carried out. As a combination, a combination of chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization) and gold sensitization is preferable. The reduction sensitization is preferably carried out during the formation of silver halide grains. The amount of chalcogen sensitizer used is preferably in the range of 10 ^{−8 to} 10 ⁻² mol, and more preferably in the range of 10 ^{−7 to} 5 × 10 ⁻³ mol, per mol of silver halide. The amount of the noble metal sensitizer used is preferably in the range of 10 ⁻⁷ to 10 ⁻² mol per mol of silver halide. The condition for chemical sensitization is p
Ag is preferably in the range of 6 to 11, and more preferably in the range of 7 to 10. The pH is preferably in the range of 4-10. The temperature is preferably in the range of 40 to 95 ° C, more preferably in the range of 45 to 85 ° C.

Various compounds can be further added to the silver halide photographic emulsion. These compounds can be added for the purpose of preventing fogging or stabilizing photographic performance in the production, storage and photographic processing of light-sensitive materials. Examples of these additives include azoles (eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles), mercaptopyrimidines, mercaptotriazines, thioketo compounds. (Eg, oxazoline thione), azaindenes (eg, triazaindene, pentaazaindenes), benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonic acid amide.

A surfactant can be added to the light-sensitive material. Surfactants are used for various purposes such as assisting coating, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic characteristics (eg, development acceleration, hardening, sensitization).

The silver halide grains can contain, in addition to the cyanochrome complex ion of the present invention, other metal complexes such as iron, ruthenium, osmium, cobalt, rhodium or iridium. Two or more kinds of complexes may be used in combination with the cyanochrome complex ion. The addition amount of the metal complex is preferably in the range of 10 ^{−9 to} 10 ⁻² mol per mol of silver halide, and more preferably in the range of 10 ^{−8 to} 10 ⁻⁴ mol per mol of silver halide. preferable. The metal complex of iron, ruthenium, osmium, cobalt, rhodium or iridium is added at the stage of preparing silver halide grains (before and after nucleation, growth, physical ripening and chemical sensitization). The metal complex may be added in portions over several times. The metal complex can be dissolved in water or an organic solvent and added. The organic solvent is preferably miscible with water. Examples of organic solvents include alcohols, ethers, glycols, ketones, esters and amides.

An iridium complex is particularly preferable as the metal complex used in combination with the cyanochrome complex ion. The iridium complex is preferably trivalent or tetravalent. Examples of the iridium complex include hexachloroiridium (III) complex salt, hexachloroiridium (VI) complex salt, hexabromoiridium (III) complex salt, hexabromoiridium (VI) complex salt.
Complex salt, hexaiodoiridium (III) complex salt, hexaiodoiridium (VI) complex salt, hexaammineiridium (I
II) complex salts and hexaammine iridium (VI) complex salts are included. As the counter cation of the iridium complex, it is preferable to use an ion that is easily miscible with water and is suitable for the precipitation operation of the silver halide emulsion. Examples of counter ions include alkali metal ions (eg, sodium ion, potassium ion, rubidium ion, cesium ion, lithium ion), ammonium ion and alkylammonium ion. The alkyl ammonium ion has been described in the above formula (II). The addition amount of the iridium complex is preferably in the range of 10 ^{−9 to} 10 ⁻⁴ mol per mol of silver halide except for the case of the hexacyanoiridium complex represented by the following formula (VII). More preferably, it is in the range of 10 ^{−8 to} 10 ⁻⁵ mol per mol of silver.

As the metal complex used in combination with the cyanochrome complex ion, a hexacyano metal complex represented by the following formula (VII) is particularly preferable. The hexacyano metal complex has the effects of obtaining a highly sensitive light-sensitive material and suppressing the occurrence of fog even when the raw light-sensitive material is stored for a long period of time.

(VII) [M (CN) ₆ ] ^{n-In the} formula, M is iron, ruthenium, osmium, cobalt, rhodium or iridium, and n is 3 or 4.

Specific examples of the hexacyano metal complex are shown below. (VII-1) [Fe (CN) ₆ ] ^4- (VII-2) [Fe (CN) ₆ ] ^3- (VII-3) [Ru (CN) ₆ ] ^4- (VII-4) [Os ( CN) ₆ ] ^4- (VII-5) [Co (CN) ₆ ] ^3- (VII-6) [Rh (CN) ₆ ] ^3- (VII-7) [Ir (CN) ₆ ] ^3-

As the counter cation of the hexacyano complex, it is preferable to use an ion which is easily miscible with water and which is suitable for the precipitation operation of the silver halide emulsion. Examples of counter ions include alkali metal ions (eg, sodium ion, potassium ion, rubidium ion, cesium ion, lithium ion), ammonium ion and alkylammonium ion. The alkyl ammonium ion has been described in the above formula (II).

The addition amount of the hexacyano metal complex is preferably in the range of 10 ^{−6 to} 10 ⁻³ mol per mol of silver halide, and 5 × 10 ^{−6 to} 5 × 10 ⁻ per mol of silver halide. More preferably, it is in the range of ⁴ moles.
The hexacyano metal complex of iron, ruthenium, osmium, cobalt, rhodium or iridium can be added at the stage of preparing silver halide grains (before and after nucleation, growth, physical ripening and chemical ripening). The hexacyano metal complex may be added in several divided portions. It is preferable that the hexacyano metal complex of iron, ruthenium, osmium, cobalt, rhodium, or iridium be introduced into the surface phase in an amount of 50% or more of the total addition amount to 50% or less of the particle volume.
Here, the surface phase of 50% or less of the particle volume means a surface portion corresponding to 50% or less of the volume of one particle. The volume of this surface phase is preferably 40% or less, more preferably 20% or less. Further, a layer containing no hexacyano metal complex of iron, ruthenium, osmium, cobalt, rhodium or iridium may be provided outside the surface phase defined here. The hexacyano metal complex of iron, ruthenium, osmium, cobalt, rhodium or iridium can be dissolved in water or an organic solvent miscible with water and added directly to the reaction solution during the formation of silver halide grains. Alternatively, it can also be introduced by adding a complex to a solution for forming silver halide grains (in a halide aqueous solution, a silver aqueous solution) or in a solution other than that to form grains.
Alternatively, the metal complex can be introduced into the grain by dissolving and adding the silver halide grain containing the metal complex in advance and depositing it on another silver halide grain.

The coating pH of the silver halide photographic light-sensitive material is
It is preferably 4.0 to 6.5, and more preferably 5.0 to 6.5. The coating film pH is the pH of all the constituent layers obtained by applying the coating liquid on the support. Therefore, the coating pH does not always match the pH of the coating liquid. The coating pH can be measured by the following method. (1) 0.05 ml of pure water is dropped on the surface of the light-sensitive material coated with the silver halide emulsion. Next, (2) After leaving for 3 minutes, a film pH measuring electrode (Gr.
S-165F) is used to measure the film pH. The above method is described in JP-A-61-245153. The coating pH can be adjusted using an acid (eg, sulfuric acid, citric acid) or an alkali (eg, sodium hydroxide, potassium hydroxide). There is no particular limitation on the method of adding the acid or alkali. As for the timing of addition,
It is the easiest to carry out when preparing the coating liquid. The acid or alkali may be added to a part of the photographic constituent layers.

A decolorizable dye may be added to the hydrophilic colloid layer of the light-sensitive material. Such dyes can be used for the purpose of preventing irradiation and halation and improving safety of safelight. Examples of decolorizable dyes include oxonol dyes and cyanine dyes. For decolorizable dyes, see European Patent 33749.
It is described on pages 27 to 76 of the specification of 0A2. The dye may be added to the hydrophilic colloid layer in the state of solid particle dispersion, and decolorized by the developing treatment. For such dyes,
It is described on pages 3 to 8 of JP-A-2-282244 and pages 3 to 11 of JP-A-3-7931. Other dyes may be added to the photosensitive material. Examples of other dyes include hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes, azomethine dyes, triarylmethane dyes and phthalocyanine dyes. The oil-soluble dye may be emulsified in water and added to the hydrophilic colloid layer.

When the above dyes are used, it is preferable to select and use a dye having an absorption such that the spectral sensitivities of the longest-wavelength photosensitive layers overlap with each other. If the optical density (logarithm of reciprocal of transmitted light, reflection density in the case of a reflective support) of the light-sensitive material is adjusted to 0.5 or more using these dyes, the sharpness of the image can be improved. it can. The optical density is measured at 680 nm or the laser wavelength used for exposure.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support.
Multilayer natural color photographic materials usually have a red sensitive emulsion layer, a green sensitive emulsion layer and a blue sensitive emulsion layer on a support. The order of arranging these layers is determined as needed. Preferred layer arrangements are, from the support side, red-sensitive, green-sensitive and blue-sensitive order, blue-sensitive layer, green-sensitive layer and red-sensitive layer, or blue-sensitive,
The order is red-sensitive and green-sensitive. Further, arbitrary emulsion layers having the same photosensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity. Further, the graininess may be further improved with a three-layer structure. A non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity. Different light-sensitive emulsion layers may be inserted between the same light-sensitive emulsion layers. A reflective layer may be provided under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer to improve the sensitivity. The reflective layer generally comprises fine grain silver halide. Generally, a cyan-forming coupler is added to the red-sensitive emulsion layer, a magenta-forming coupler is added to the green-sensitive emulsion layer, and a yellow-forming coupler is added to the blue-sensitive emulsion layer. Depending on the case, different combinations may be adopted. For example, an infrared-sensitive layer may be combined to form a pseudo color photosensitive material or a semiconductor laser exposure photosensitive material.

Various color couplers can be used in the photographic light-sensitive material. For color couplers,
It is described in various patent documents. These references are Research Disclosure, 176, 17643 (19).
78), section VII-C to G. Regarding yellow couplers, U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024 and 440.
No. 1752, Japanese Patent Publication No. 58-10739,
There is a description in each of British Patent Nos. 142520 and 1476760.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferably used. For magenta couplers, US Pat.
1432, 3725067 and 4310619.
No. 4351897, No. 4500630, No. 45
40654 and European Patent No. 73636, Research Disclosure, No. 24220 (198)
4), No. 24230 (1984), JP-A-60-33.
No. 552 and 60-43659. Phenol-based and naphthol-based compounds are preferably used as the cyan coupler. Regarding cyan couplers, US Pat. Nos. 2,369,929 and 27,721.
62, 2801171, 2895826, 3446622, 3758, 309, 3772.
No. 002, No. 4052212, No. 4146396,
No. 4228233, No. 4296200, and No. 4333.
999, 4327173, 4334011,
No. 4,427,767, No. 4,451,559, West German Patent 3
329729, European Patent 121365A and 1
No. 61626A is described in each specification.

Colored couplers may be used to correct unwanted absorption of the color forming dye. For colored couplers, Research Disclosure, 176,
17643 (1978), section VII-G, US Pat.
No. 004926, No. 4138258, No. 416367
No. 0 and British Patent No. 1146368, and Japanese Patent Publication No. 57-39413. A coupler in which the color forming dye has a suitable diffusibility may be used. Such couplers are described in US Pat. No. 4,366,237, British Patent 2125570, European Patent 96570 and West German Patent 3345533.

Polymerized dye forming couplers can also be used. For such couplers, U.S. Pat. Nos. 3,451,820, 4,802,211, and 436 are described.
No. 7282 and British Patent No. 2102173 are described. Couplers that release a photographically useful residue upon coupling can also be used. DIR couplers that release development inhibitors are disclosed in Research Disclosure, 176, 17643 (1978), Section VII-F, JP-A-57-151944.
Nos. 57-154234 and 60-18424.
No. 8 and US Pat. No. 4,248,962. For couplers that release a nucleating agent or a development accelerator imagewise during development, see British Patent 209714.
No. 0 and No. 2131188, JP-A-59-
157638 and 59-170840.

Further, competitive couplers, multi-equivalent couplers,
A DIR redox compound or a DIR coupler-releasing coupler, a coupler that releases a dye that restores color after withdrawal, a bleach accelerator-releasing coupler or a ligand-releasing coupler may be used. US Patent 41 for competitive couplers
It is described in the specification of No. 30427. For multi-equivalent couplers, U.S. Pat. Nos. 4,283,472 and 4,310,618.
And No. 4338393. D
Regarding the IR redox compound or the DIR coupler-releasing coupler, JP-A-50-24252 and JP-A-6-242252.
It is described in each publication of 0-185950. For couplers that release dyes that recolor after release, see European Patent 173.
No. 302A specification. Research Disclosure 1144 for bleach accelerator releasing couplers
No. 9, 24241, and JP-A No. 61-201247. Ligand releasing couplers are described in US Pat. No. 4,553,477.

The above couplers can be introduced into the light-sensitive material by a generally known oil-in-water dispersion method. In the oil-in-water dispersion method, a high boiling organic solvent is used. The high boiling point organic solvent is described in US Pat. No. 2,322,027. The boiling point of the organic solvent is preferably 175 ° C. or higher under normal pressure. As the high boiling point organic solvent, phthalates,
Phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols, phenols, aliphatic carboxylic acid esters, aniline derivatives and hydrocarbons are used.

Examples of phthalic acid esters are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,
4-di-t-amylphenyl) phthalate, bis (2,
4-di-t-amylphenyl) isophthalate and bis (1,1-diethylpropyl) phthalate are included. Examples of phosphoric or phosphonic acid esters are triphenyl phosphate, tricresyl phosphate,
Included are 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate and di-2-ethylhexyl phenyl phosphate. Examples of benzoic acid esters include 2-ethylhexyl benzoate, dodecyl benzoate and 2-ethylhexyl benzoate.
Included is ethylhexyl-p-hydroxybenzoate. Examples of amides include N, N-diethyldodecane amide, N, N-diethyllaurylamide and N-tetradecylpyrrolidone. An example of alcohols is isostearyl alcohol. Examples of phenols are
It is 2,4-di-tert-amylphenol. Examples of aliphatic carboxylic acid esters include bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate and trioctyl citrate. An example of an aniline derivative is N, N-dibutyl-2-butoxy-5-tert-octylaniline. Examples of hydrocarbons include paraffin, dodecylbenzene and diisopropylnaphthalene.

In addition to the high boiling point organic solvent, an auxiliary solvent may be used. The boiling point of the auxiliary solvent is preferably 30 ° C. or higher, more preferably 50 to 160 ° C. As the auxiliary solvent, it is preferable to use an organic solvent. Examples of co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The coupler may be added to the light-sensitive material by a latex dispersion method. For latex dispersion method,
U.S. Pat. No. 4,199,363, West German Patents 2541274 and 2541230 are described in the respective specifications. A color image storability improving compound may be added together with the coupler. Regarding the compound for improving the preservation of color image, European Patent 277589
There is a description in A2 specification. The compound for improving color image storability is
A combination with a pyrazoloazole coupler or a pyrrolotriazole coupler is particularly preferable. The above compound chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound. Alternatively, the above compound chemically bonds with the oxidation product of the aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound. This makes it possible to prevent stains from being generated due to the formation of a color-forming dye due to the reaction between the coupler and the color-developing agent remaining in the film during storage after the treatment. An antifungal agent can be added to the light-sensitive material. The fungicide prevents various molds and bacteria from propagating in the hydrophilic colloid layer and deteriorating the image. The antifungal agent is described in JP-A-63-271247.

Each photographic functional layer is coated on a support. Both flexible and rigid supports are available. The flexible support is made of plastic film, paper or cloth. The rigid support consists of glass, earthenware or metal. Useful flexible supports are plastic films and variator layers of semi-synthetic or synthetic polymers or paper coated or laminated with alpha-olefin polymers (eg polyethylene, polypropylene, ethylene / butene copolymers). The plastic film is
Manufactured from cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate or polycarbonate.
The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of the support is generally subbed to improve its adhesion to the photographic emulsion layers. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation or flame treatment before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used.
Examples of coating methods include dip coating, roller coating, curtain coating and extrusion coating. Multiple layers may be applied simultaneously. The method of simultaneous multi-layer coating is described in US Pat. Nos. 2,681,294, 2,761,791 and 3,508.
No. 947 and No. 3526528 are described.

The present invention can be applied to various color light-sensitive materials. Various light-sensitive materials include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type light-sensitive materials and heat development type color light-sensitive materials. Including. The present invention can be applied to black-and-white light-sensitive materials. Black and white photosensitive material is X
It can also be used as a line film. When used as a black-and-white light-sensitive material, a black image may be formed by mixing three-color couplers. Also, a black color coupler can be used. The mixing of three color couplers is described in Research Disclosure, No. 17123 (1978).
Black color couplers are described in US Pat. No. 4,126,461 and British Patent No. 2,102,136. Film for plate making such as squirrel film or scanner film, X-ray film for direct / indirect medical treatment or industry, negative black and white film for photography, black and white photographic paper, CO
The present invention can be applied to M or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

The photographic light-sensitive material of the present invention can be applied to a color diffusion transfer photographic method. Color diffusion transfer photography has a peel-apart type and a peel-free type film unit. Regarding the peeling-free type, Japanese Patent Publications No. 46-16356, No. 48-33697, JP-A No. 50-13040 and British Patent No. 133052.
There is a description in No. 4 specification. In any of the above types,
It is preferred to use a polymeric acid layer protected by a neutralization timing layer. The polymer acid layer has a function of widening the allowable range of processing temperature. The polymer acid may be used by adding it to any layer of the color diffusion transfer photographic light-sensitive material, or may be put in a processing solution container as a developing solution component.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material is used as an irradiation light source or a writing light source. Natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and flash light sources (eg strobes, metal burning flash bulbs) are commonly used. A laser (a gas, a dye solution or a semiconductor) that emits light in a wavelength range from ultraviolet to infrared, a light emitting diode, and a plasma light source can also be used as the recording light source. In addition, a phosphor screen (eg, CRT) emitted from a phosphor excited by an electron beam, liquid crystal (LCD), or lanthanum-doped lead titan zirconate (PLZ).
It is also possible to use an exposure means in which a linear or planar light source is combined with the micro shutter array utilizing T). If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used for the developing treatment is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds and p-phenylenediamine compounds can be used. A p-phenylenediamine compound is preferred. Examples of color developing agents are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino. -N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
Includes toluene sulfonate. Since diamines are generally more stable in the salt state than in the free state, they are preferably used in the salt state.

The color developer generally contains a pH buffer (eg,
Alkali metal carbonates, borates, phosphates) and development inhibitors or antifoggants (eg bromide, iodide,
Benzimidazoles, benzothiazoles, mercapto compounds). If necessary, preservatives (eg, hydroxylamine, sulfurous acid), organic solvents (eg, triethanolamine, diethylene glycol), development accelerators (eg,
Benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines), dye forming couplers, competing couplers, nucleating agents (eg sodium boron hydride),
Auxiliary developing agent (eg, 1-phenyl-3-pyrazolidone),
Viscosity imparting agents, chelating agents (eg, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid) and an antioxidant (described in West German Patent No. 2622950) may be added to the color developer.

In the development processing of the reversal color light-sensitive material, black and white development is usually carried out and then color development is carried out. The black and white developer contains a black and white developer. Examples of black and white developers include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone) and aminophenols (eg, N-methyl-p-aminophenol). Be done. Two or more kinds of black and white developers may be used in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process.
In order to speed up the processing, a method of carrying out a bleach-fixing processing after the bleaching processing may be adopted. As the bleaching agent, polyvalent metal compounds, peracids, quinones and nitroso compounds are used. Polyvalent metals are generally iron (II), iron (III)
It is cobalt (III), chromium (IV) or copper (II).
Examples of bleaching agents are ferricyanide, dichromate, iron
(III) or cobalt (III) organic complex salts, persulfate, manganate and nitrosophenol are included. The above organic complex salts include aminopolycarboxylic acids (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid) and other organic acids (eg, citric acid, tartaric acid, apple). Acid). Ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid (III) salt and persulfate salt are preferably used because they can be rapidly processed and have little environmental pollution. Ethylenediaminetetraacetic acid iron (I
The II) complex salts are particularly useful in stand-alone bleaching solutions as well as in one-bath bleach-fixing solutions.

If necessary, a bleaching accelerator can be added to the bleaching solution, the bleach-fixing solution and their pre-bath.
Examples of the bleaching accelerator include compounds having a mercapto group or a disulfide group, thiazolidine derivatives, thiourea derivatives, iodides, polyethylene oxides, polyamine compounds, iodide and bromide ions.
The compound having a mercapto group or a disulfide group,
It is preferably used because it has a large accelerating effect. Regarding the compound having a mercapto group or a disulfide group, U.S. Pat. No. 3,839,858, West German Patents 1,290,812 and 20,599,988, JP-A No. 53-284.
No. 26, No. 53-32736, No. 53-57831.
No. 37, No. 37-418, No. 53-65832, No. 53
No. 72623, No. 53-95630, No. 53-95.
No. 631, No. 53-104232, No. 53-1244.
No. 24 and No. 53-141623, Research Disclosure, No. 17129 (1978). For the thiazolidine derivative, see JP-A-50.
No. 140129 discloses. Regarding the thiourea derivative, JP-B-45-8506 and JP-A-52-20
No. 832 and No. 53-32735, and U.S. Pat. No. 3,706,561. Regarding iodide, West German Patent No. 1127715, JP-A-58-
It is described in Japanese Patent No. 16235. Regarding polyethylene oxides, West German Patents 966410 and 27
No. 48430 is described in each specification. The polyamine compound is described in JP-B-45-8836. Regarding other bleaching accelerators, JP-A-49-42
No. 434, No. 49-59644, No. 53-94927.
No. 54-35727, No. 55-26506, and No. 58-163940.

These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color light-sensitive material for photographing, the use of a bleaching accelerator is particularly effective. A fixing agent is used in the bleach-fixing process or the fixing process. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas and iodides (used in large amounts). Thiosulfate is commonly used. The bleach-fixing solution and the fixing solution may contain a preservative. Examples of preservatives include sulfites, bisulfites and carbonyl bisulfite adducts.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilizing treatment are usually carried out. Various additives may be used in the washing treatment liquid and the stabilizing treatment liquid for the purpose of preventing precipitation and conserving water. For example, a water softener, an insecticide, an antifungal agent, a metal salt (eg, magnesium salt, aluminum salt, bismuth salt), a surfactant or a hardener can be added to the treatment liquid, if necessary. . Water softeners are generally chelating agents and are used to prevent precipitation. Examples of the hardener include inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid and organic phosphoric acid. Insecticides and fungicides are used to prevent the development of various bacteria, algae and mold. The surfactant is used to prevent drying load and unevenness. For other additives, see West, Photograph Science Science and Engineering (LE West, Photo Sci. En.
g. ), Vol. 6, 344 (1965). The addition of a chelating agent or antifungal agent is particularly effective.

In the water washing step, generally, a plurality of tanks are subjected to countercurrent water washing to save water. A multi-stage countercurrent stabilization treatment process may be performed instead of the water washing process. The multistage countercurrent stabilization treatment process is described in JP-A-57-8543. The multi-stage countercurrent stabilization treatment process requires 2 to 9 baths of countercurrent baths. In addition to the above additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, a buffering agent or aldehyde (eg, formalin) for adjusting the membrane pH (generally pH 3 to 9) is added to the stabilizing bath. Examples of the above buffer include borate, metaborate,
Includes borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids and combinations thereof. In addition, if necessary, a chelating agent (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid), insecticide (eg, benzisothiazolinone, Irithiazolone,
4-thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole), a surfactant, an optical brightener and a hardener may be added to the stabilizing bath. You may use together 2 or more types of additives.

A membrane pH adjuster may be added to the treatment liquid.
An ammonium salt is preferably used as the membrane pH adjuster after such treatment. Examples of ammonium salts include
Included are ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite and ammonium thiosulfate. For color sensitizers for photography, the (washing-stabilizing) step after fixing which is usually performed is
It is also possible to replace with the above-mentioned stabilization step and water washing step (water saving treatment). The addition of formalin to this stabilizing bath can be omitted if the magenta coupler is 2 equivalents. The washing and stabilizing processing times are determined by the type of photosensitive material and processing conditions. The treatment time is generally 20 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and accelerating the processing. In that case, it is preferable to use various precursors of color developing agents. Examples of precursors include indoaniline-based compounds, Schiff base-type compounds, aldol compounds, metal complex salts, urethane-based compounds and salt-type compounds. The indoaniline compound is described in US Pat. No. 3,342,592. The Schiff base type compound is described in US Pat. No. 3,342,599 and Research Disclosure, 14850 and 15159. The aldol compound is described in Research Disclosure, 13924. For the metal complex salt, see US Pat. No. 37194.
No. 92 specification. The urethane compound is described in JP-A-53-135628. Regarding the salt type compound, JP-A-56-6235 and JP-A-56-6235
-16133, 56-54430, 56-59.
No. 232, No. 56-67842, No. 56-81837.
No. 56, No. 56-83734, No. 56-83735, No. 56-83736, No. 56-89735, No. 56-
106241, 56-107236, 57-8
3565 and 57-97531. The silver halide color light-sensitive material may contain 1-phenyl-3-pyrazolidones for the purpose of promoting color development. Regarding 1-phenyl-3-pyrazolidones, JP-A-56-64339 and JP-A-57-1445.
No. 47, No. 57-211147, No. 58-50532.
No. 58, No. 58-50534, No. 58-50533, No. 58-50535, No. 58-50536 and No. 5
It is described in each publication of 8-115438.

Various processing solutions are generally used at 10 to 50 ° C. The standard temperature is 33 to 38 ° C. The temperature may be raised above the standard temperature to accelerate the treatment and shorten the treatment time. On the contrary, the temperature may be lowered to improve the image quality and the stability of the processing liquid. In order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification may be performed. For such processing, West German Patent 2226
770 and US Pat. No. 3,674,499. If necessary, heaters in various treatment baths,
A temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig or a squeegee may be provided.

In continuous processing, a replenisher for each processing solution may be used to prevent fluctuations in the composition of the solution. Preventing compositional variations provides a consistent finish. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction. When the light-sensitive material is color paper, the bleach-fixing process can be carried out according to a very general method. When the light-sensitive material is a color photographic material for photographing, a bleach-fixing process can be carried out if necessary.

[0174]

【Example】

[Example 1] "Emulsion A: Preparation of silver chloride cubic emulsion" To 845 ml of an aqueous solution containing 4.5 g of sodium chloride, 25 g of deionized gelatin was added and dissolved, and the solution was dissolved at 0.21 M silver nitrate ( Solution 1) 140 ml and 0.2
140 ml of 1M sodium chloride aqueous solution (solution 2) was quantitatively added by the double jet method for 10 minutes. After 10 minutes, 2.
320 ml of 2M silver nitrate aqueous solution (solution 3) and 320 ml of 2.2M sodium chloride aqueous solution (solution 4) were further quantitatively added by the double jet method for 35 minutes. After 5 minutes from the completion of the addition, the temperature was lowered to 35 ° C., soluble salts were removed by an ordinary precipitation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and sodium chloride and phenol were further added, The pH was adjusted to 6.5. The obtained grains are monodisperse silver chloride cubes with a side length of 0.5 μm (variation coefficient 15
%)Met.

"Emulsions B-1 to 3: (NH ₄ ) ₂ [RhC
Preparation of Silver Chloride Cubic Emulsion Doped with l ₅ (H ₂ O)] In Solution 4 of Emulsion A, 1 × 10 ⁻⁸ , 1 × 10 ⁻⁷ and 1 × 10 ⁻⁶ mol per mol of silver added, respectively. Of (N
Emulsion A except that it contains H ₄ ) ₂ [RhCl ₅ (H ₂ O)]
Emulsions B-1, B-2 and B-3 were respectively prepared in the same manner as in.

"Emulsions C-1 to 3: K ₃ [Cr (CN)
₆ ] Preparation of a silver chloride cubic emulsion doped with "4", to the solution 4 of the emulsion A, 1 × 10 ^-8 for each mol of silver added,
1 × 10 ⁻⁷ and 1 × 10 ⁻⁶ mol of K ₃ [Cr (CN)]
Except containing _6] in the same manner as Emulsion A, Emulsion C-1, C
-2 and C-3 were prepared respectively.

Emulsions A, B-1 to 3 and C-1 to
Gelatin, sodium dodecylbenzenesulfonate were added to 3 respectively, and gelatin, polymethylmethacrylate particles, and 2,4-dichloro-6-hydroxy- were formed on a triacetyl cellulose film support having an undercoat layer.
Coating samples 1 to ² were coated with a protective layer containing s-triazine sodium salt by an extrusion method at a silver amount of 2 g / m ² , respectively.
7 were obtained respectively.

These samples were exposed for sensitometry (10 seconds) through an optical wedge, and then M of the following formulation was used.
After developing with an AA-1 * developing solution at 20 ° C. for 5 minutes, it was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured.

MAA-1 * Developer ────────────────────────────────────────── ────────────────────────────────Metol 2.5g L-Ascorbic acid 10.0g Nabox 35.0g NaCl 0. 58g Add water 1 liter ─────────────────────────────────────

The samples were evaluated as follows. Fog was determined by the minimum optical density of the sample. Sensitivity is fog +
It was expressed by the reciprocal of the exposure amount required to obtain an optical density of 0.5, and was expressed as a relative value with the value of Sample 1 being 100.
The gradation represents the slope of the straight line portion of the characteristic curve, and the larger the gradation, the harder the gradation. The foot density is 0.8 of the exposure amount that gives the above sensitivity.
It represents the optical density obtained by subtracting the minimum optical density from the optical density when a double exposure amount is given, and the lower the value, the shorter the characteristic curve. The results are shown in Table 1. The first
The amount of dopant added in the table is the molar amount per mol of silver halide.

[0181]

[Table 1] Table 1 ──────────────────────────────────── Sample dopant fog Sensitivity Gradation Concentration number Compound addition amount ───────────────────────────────────── 1 None 0.06 100 2.6 0.32 2 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-8 0.05 56 56 1.0 0.33 3 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-7 0.05 39 3.2 0.27 4 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-6 0.05 5 4.1 0.21 5 K ₃ [Cr (CN ) ₆ ] 1 x 10 ^-8 0.05 74 2.3 0.32 6 K ₃ [Cr (CN) ₆ ] 1 x 10 ^-7 0.05 47 47 2.6 0.28 7 K ₃ [Cr (CN) ) ₆ ] 1 × 10 ^-6 0.05 10 10 5.7 0.07 ───────────────────────────────── ────

Example 2 Emulsion A prepared in Example 1
For B-2, B-3, C-2 and C-3, 1 × 10 ⁻² mol of silver bromide fine grain emulsion per mol of silver, 2.5 × 10 ⁻⁶
Optimum chemical sensitization was carried out at 60 ° C. by adding mol of sodium thiosulfate and 3 × 10 ⁻⁷ mol of chloroauric acid, respectively. Then, coating was performed in the same manner as in Example 1 to obtain coated samples 8 to 12, respectively. These samples were evaluated as in Example 1. The results are shown in Table 2.

[0183]

[Table 2] Table 2 ──────────────────────────────────── Sample dopant fog Sensitivity Gradation Concentration number Compound addition amount ───────────────────────────────────── 8 None 0.10 100 2.2 0.36 9 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ⁻⁷ 0.08 40 2.6 0.32 10 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-6 0.09 5 3.7 0.23 11 K ₃ [Cr (CN) ₆ ] 1x 10 ^-7 0.07 64 4.0 0.25 12 K ₃ [Cr (CN) ₆ ] 1x 10 ^-6 0.05 9 6.4 0.15 ─────────────────────────────────────

Example 3 Emulsions A, B-3 and C-3 prepared in Example 1 were each added with a mercapto heterocyclic compound (III-2-2) at 5 × 10 ^-3 per mol of silver.
After adding mols, coating was carried out in the same manner as above to obtain coating samples 13 to 15. Also, for emulsions A, B-3 and C-3,
The tetrazaindene compound (IV-1) was added in an amount of 5 × 10 ⁻³ mol per mol of silver and then coated in the same manner as above to obtain coated samples 16 to 18, respectively. These samples were evaluated as in Example 1. Furthermore, the maximum optical density (Dmax) and storage stability (ΔlogE) of each sample were examined. ΔlogE represents the difference between the sensitivity of the sample after heating at 50 ° C. for 3 days after coating and the sensitivity of the sample immediately after coating in terms of exposure dose. The results are shown in Table 3. In Table 3,
The results of Application Samples 1, 4 and 7 are also reproduced for reference.

[0185]

[Table 3] Table 3 ──────────────────────────────────── Sample dopant Additive Fog Sensitivity Additive concentration Dmax ΔlogE ───────────────────────────────────── 1 None None 0.06 100 2.6 0.32 1.85 + 0.94 4 Rh None 0.05 5 4.1 0.21 1.35 +0.44 7 Cr None 0.05 10 5.7 0.07 1.40 +0.25 13 None III 0.05 115 2.8 0.27 1.98 +0.47 14 Rh III 0.05 8 4.4 0.20 2.10 +0.28 15 Cr III 0.05 11 5.9 0.06 2.12 + 0.12 16 None IV 0.05 113 2.7 0.32 1.99 +0.42 17 Rh IV 0.05 7 4.3 0.21 2.08 +0.33 18 Cr IV 0.05 11 5.8 0.06 2.11 +0.14 ──────────────────── ───────────────── (Note) Rh: (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] is used in an amount of 1 × 10 ^-6 mol per mol of silver Cr: Use K ₃ [Cr (CN) ₆ ] 1 × 10 ^-6 mol per mol of silver II I: mercaptoheterocyclic compound III-2-2 is used at 5 × 10 ^-3 mol per mol of silver IV: tetrazaindene compound IV-1 is 5 per mol of silver
× 10 ^-3 mol use

Example 4 Emulsions A, B-3 and C-3 prepared in Example 1 were mixed with 1 × 10 3 per mol of silver.
Optimal chemical sensitization was carried out at 60 ° C. by adding ⁻² mol of silver bromide fine grain emulsion, 2.5 × 10 ⁻⁶ mol of sodium thiosulfate and 3 × 10 ⁻⁷ mol of chloroauric acid. afterwards,
After adding 5 × 10 ⁻³ mol of the mercapto heterocyclic compound (III-2-2) per mol of silver, coating was performed in the same manner as above to obtain coated samples 19 to 21, respectively. Similarly, to the emulsions A, B-3 and C-3 after chemical sensitization, the tetrazaindene compound (IV-1) was added in an amount of 5 × 10 ⁻³ mol per mol of silver, followed by the same method as above. Apply sample 2
2 to 24 were obtained respectively. These samples were evaluated as in Example 1. Furthermore, the maximum optical density (Dmax) of each sample
The storage stability (ΔlogE) was examined. ΔlogE represents the difference between the sensitivity of the sample after heating at 50 ° C. for 3 days after coating and the sensitivity of the sample immediately after coating in terms of exposure dose.
The results are shown in Table 4. In Table 4, the results of coated samples 8, 10 and 12 are also reproduced for reference.

[0187]

[Table 4] Table 4 ──────────────────────────────────── Sample dopant Additive Fog Sensitivity Additive concentration Dmax ΔlogE ───────────────────────────────────── 8 None None 0.10 100 2.2 0.36 1.85 + 0.34 10 Rh None 0.09 5 3.7 0.23 1.65 +0.24 12 Cr None 0.05 9 6.4 0.15 1.60 +0.15 19 None III 0.08 108 2.5 0.42 1.88 +0.23 20 Rh III 0.07 7 4.6 0.22 2.12 +0.18 21 Cr III 0.07 10 6.7 0.13 2.14 + 0.09 22 None IV 0.08 109 2.7 0.44 1.89 +0.22 23 Rh IV 0.07 9 4.5 0.23 2.10 +0.18 24 Cr IV 0.06 11 6.6 0.12 2.12 +0.08 ──────────────────── ───────────────── (Note) Rh: (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] is used in an amount of 1 × 10 ^-6 mol per mol of silver Cr: _{K 3 [Cr (CN) 6} ] per mole of silver 1 × 10 ^-6 mol using III: mercapto heterocyclic compound III-2-2 per mole silver 5 × 10 ^-3 moles IV: silver tetrazaindene compound IV-1 per mole 5
× 10 ^-3 mol use

[Example 5] "Preparation of silver chloride 99% emulsion sample" [0188] An emulsion was prepared in the same manner as in the emulsion A of Example 1, and then 1 x per 1 mol of silver.
Optimal chemical sensitization was carried out at 60 ° C. by adding 10 ⁻² mol of silver bromide fine particles, sodium thiosulfate and chloroauric acid. Then, as in Example 3, the tetrazaindene compound (IV-1) was added before coating. It was applied in the same manner as in Example 1. The coating pH was measured by the method described in the present specification by adjusting the pH by adding sulfuric acid and sodium hydroxide to the coating solution. At this time, according to Table 5, (NH ₄ ) ₂ [RhCl ₅
(H ₂ O)] and K ₃ [Cr (CN) ₆ ] were added to Solution 4 of Emulsion A in an amount of 1 × 10 ⁻⁶ mol per mol of silver, and addition was further performed, and further 1 × 10 ⁻ per mol of silver. ⁶ moles of K ₂
[IrCl ₆ ] and 1 × 10 -5 mol of K ₄ [Fe (C
N) ₆ ] was added to Solution 4 of Emulsion A to obtain Coating Samples 25 to 30 for the added emulsion.

Sensitometric exposure (10 seconds) was applied to these samples through an optical wedge, and then M of the above formulation was used.
After developing with an AA-1 * developing solution at 20 ° C. for 5 minutes, it was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured.
Regarding the sensitivity, the value was the same as that of Sample 25 except that the value of Sample 25 was 100. Fog, gradation, foot density, Dmax
And ΔlogE were examined respectively. Fog was determined by the minimum optical density of the sample.

"Preparation of Silver Chloride 50% Emulsion Sample" To 845 ml of an aqueous solution containing 2.3 g of sodium chloride and 4.6 g of potassium bromide, 25 g of deionized gelatin was added and dissolved, and the solution was stirred at 0. 140 ml of 18M silver nitrate aqueous solution (solution 5) and 0.10M sodium chloride and 0.10M potassium bromide mixed aqueous solution (solution 6)
140 ml was quantitatively added by the double jet method for 10 minutes. After 10 minutes, a 2.2M silver nitrate aqueous solution (solution 7) 320
ml and 2.2M aqueous sodium chloride solution (solution 8) 320
Further, a fixed amount of 70 ml was added by the double jet method for 70 minutes. After 5 minutes from the completion of the addition, the temperature was lowered to 35 ° C., soluble salts were removed by an ordinary precipitation method, the temperature was raised again to 40 ° C., gelatin was additionally added to dissolve, and sodium chloride, potassium bromide and phenol were added. Was added to adjust the pH to 6.5. The obtained grains were monodisperse silver chlorobromide cubes with a side length of 0.5 μm (variation coefficient: 17%). Sodium thiosulfate, chloroauric acid and potassium thiocyanide were added to this silver chlorobromide emulsion for optimum chemical sensitization at 60 ° C. Then, as in Example 3, the tetrazaindene compound (IV-1) was added before coating. It was applied in the same manner as in Example 1. The coating pH was also adjusted by the above method. At this time, for the emulsion before chemical sensitization, according to Table 5, (NH ₄ ) ₂ [RhCl ₅ H ₂
O)] and K ₃ [Cr (CN) ₆ ] are added to the solution 8 in an amount of 1 × 10 ⁻⁶ mol per mol of silver, and the addition is performed.
Solution 8 of 1 × 10 ⁻⁶ mol K ₂ [IrCl ₆ ] and 1 × 10 ⁻⁵ mol K ₄ [Fe (CN) ₆ ] per mol silver.
In addition to the above, coating samples 31 to
Got 6.

Sensitometric exposure (10 seconds) was applied to these samples through an optical wedge, and then M of the following formulation was used.
After developing with an AA-1 developer at 20 ° C. for 10 minutes, it was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured. Regarding the sensitivity, the fog, the gradation, the foot density, and the foot density are the same as above except that the value of the sample 31 is expressed as a relative value.
Dmax and ΔlogE were examined respectively.

MAA-1 Developer ────────────────────────────────────────── ─────────────────────────────── METOH 2.5g L-Ascorbic acid 10.0g Nabox 35.0g KBr 1.0g Add 1 liter of water ────────────────────────────────────

"Preparation of silver bromide 100% (silver chloride 0%) emulsion sample" To 870 ml of water, 36 g of deionized gelatin and 0.25 g of potassium bromide were added and dissolved. 0.088 with stirring in this gelatin aqueous solution kept at 75 ° C.
36 ml of M silver nitrate aqueous solution (solution 9) and 36 ml of 0.088 M potassium bromide aqueous solution (solution 10) were quantitatively added by the double jet method for 10 minutes, and subsequently 176 ml of each of solution 9 and solution 10 was added by the double jet method for 7 minutes. Was added.
After that, 0.82 M silver nitrate aqueous solution (solution 11) 898 m
First, the flow rate was accelerated from a flow rate of 0.53 ml / min for 95 minutes, and at the same time, a 0.90 M potassium bromide aqueous solution (solution 12) was controlled to maintain a silver potential of +120 mV (vs. saturated calomel electrode). And added.
After 5 minutes from the completion of the addition, the temperature was lowered to 35 ° C., soluble salts were removed by an ordinary precipitation method, and then the temperature was raised to 40 ° C.
g Gelatin was added and dissolved, and potassium bromide and phenol were further added to adjust the pH to 6.5.
The resulting grains were monodisperse silver bromide cubes with a side length of 0.5 μm (variation coefficient 13%).

Sodium thiosulfate, chloroauric acid and potassium thiocyanide were added to this silver bromide emulsion to perform optimum chemical sensitization at 60 ° C. Then, as in Example 3, the tetrazaindene compound (IV-1) was added before coating. It was applied in the same manner as in Example 1. The coating pH was also adjusted by the above method. At this time, according to Table 5, (NH ₄ ) ₂ [RhCl
₅ (H ₂ O)] and K ₃ [Cr (CN) ₆ ] were added to the solution 12 at 1 × 10 −5 or 1 × 10 ⁻⁶ mol per mol of silver. These samples were exposed for sensitometry (10 seconds) through an optical wedge, then developed with the above-prepared MAA-1 developer at 20 ° C. for 10 minutes, and then stopped, fixed, washed with water and dried by a conventional method. Then, the optical density was measured. Regarding the sensitivity, fog, gradation, toe density, Dmax and ΔlogE were examined in the same manner as described above except that the value of Sample 37 was expressed as a relative value with 100 being the value. The results are shown in Table 5.

[0195]

[Table 5] Table 5 ──────────────────────────────────── Specimen Chloride Dopant Coating Fog Sensitivity Tonal concentration Dmax ΔlogE Silver I II pH ──────────────────────────────────── 25 99 Rh None 5.7 0.07 100 4.5 0.23 2.10 +0.18 26 99 Rh Ir 5.8 0.07 103 4.7 0.21 2.12 +0.15 27 99 Rh Fe 5.9 0.06 101 4.8 0.22 2.11 +0.17 28 99 Cr no 5.8 0.06 125 6.6 0.12 2.12 +0.08 29 99 Cr Cr Ir 5.7 0.07 128 6.8 0.10 2.13 +0.06 30 99 Cr Cr Fe 5.9 0.06 124 6.7 0.11 2.13 +0.07 31 50 Rh None 5.6 0.06 100 4.0 0.26 1.99 +0.15 32 50 Rh Ir 5.8 0.08 105 4.2 0.25 2.02 +0.12 33 50 Rh Fe 5.7 0.07 102 4.3 0.25 2.05 +0.13 34 50 Without Cr 5.7 0.07 119 4.3 0.19 2.00 +0.12 35 50 Cr Ir 5.8 0.07 122 4.5 0.1 7 2.07 +0.10 36 50 Cr Cr 5.9 0.08 120 4.6 0.18 2.06 +0.12 37 0 Rh * None 5.8 0.07 100 3.0 0.28 2.01 +0.30 38 0 Rh None 5.7 0.08 13 3.9 0.25 1.95 +0.30 39 0 Cr * None 5.9 0.08 180 2.6 0.29 2.00 +0.31 400 Cr None 5.8 0.07 60 3.0 0.28 1.97 +0.30 ─────────────────────────────────── ── (Note) Rh: (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] is used at 1 × 10 ^-6 mol per 1 mol of silver Rh *: (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 x 10 ^-7 mol is used per mol of silver Cr: K ₃ [Cr (CN) ₆ ] is used at 1 x 10 ^-6 mol per mol of silver Cr *: K ₃ [Cr (CN) ₆ ] is used as silver 1 mol per 1 × 10 ^-7 moles Ir: K ₂ [IrCl _6] per mol of silver 1 × 10 ^-6 moles of _{Fe: K 4 [Fe (CN} ) 6] per mol of silver 1 × 10 ^-6 to Use mole

Example 6 “Preparation of Emulsion D” Aqueous gelatin solution kept at 40 ° C. (5 × 1 of tetrazaindene compound (IV-1) per mol of silver)
(0 ^-3 mol contained), and 4 mol per mol of silver nitrate aqueous solution and silver.
× 10 -5 mol of (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)]
An aqueous sodium chloride solution containing P was added at the same time for 7 minutes, and the silver potential was controlled to 95 mV during that period to prepare 0.12 μm of particles in the core portion. After that, 1.2 × 10 ⁻⁴ mol of (N 2
An aqueous sodium chloride solution containing H ₄ ) ₂ [RhCl ₅ (H ₂ O)] was simultaneously added over 14 minutes, and the potential during that period was adjusted to 95
Cubic silver chloride particles having an average particle size of 0.15 μm were prepared by controlling the mV.

"Preparation of Emulsion E" (NH ₄ ) ₂ [RhCl
Emulsion M except that the addition amount of ( ₅ (H ₂ O)] (both core portion and shell portion) is 6.5 × 10 ⁻⁵ mol per mol of silver.
Prepared in a similar manner.

[Preparation of Emulsion F] (NH ₄ ) ₂ [RhCl
₅ (H ₂ O)] instead of the compound K ₃ [Cr (C
N) ₆ ] was used and prepared in the same manner as in Emulsion M.

[Preparation of Emulsion G] (NH ₄ ) ₂ [RhCl
₅ (H ₂ O)] instead of the compound K ₃ [Cr (C
N) ₆ ] was used and prepared in the same manner as in Emulsion N.

"Preparation of Emulsion H" (NH ₄ ) ₂ [RhCl
₅ (H ₂ O)] in place of sodium chloride aqueous solution, instead of using 8 × 10 ⁻⁵ mol of K ₃ [Cr
An aqueous solution of sodium chloride containing (CN) ₆ ] in the core part,
2.4 × 10 ⁻⁴ mol of K ₃ [Cr (C (C
N) ₆ ] was used in the same manner as in Emulsion M, except that an aqueous sodium chloride solution containing N) ₆ ] was used for the shell portion to form grains.

[Preparation of Emulsion I] (NH ₄ ) ₂ [RhCl
₅ (H ₂ O)] in place of sodium chloride solution, 1.3 × 10 ⁻⁴ mol of K ₃ [C
r (CN) ₆ ] was used in the same manner as Emulsion N except that an aqueous sodium chloride solution containing r (CN) ₆ ] was used.

(Preparation of Coating Sample) First Photosensitive Emulsion Layer The following additives were added to the above emulsion D and coated so that the silver amount was 1.7 g / m ² (gelatin was 0.9 g / m ² ).

──────────────────────────────────── 1st photosensitive emulsion layer ───── ─────────────────────────────── Polyethyl acrylate latex (average particle size 0.05 μm) 0.6 g / m ² 4 -Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 30 mg / m ² Compound A 40 mg / m ² Compound B 10 mg / m ² Hardener (Compound C) 98 mg / m ² Compound D 53 mg / m ² ────────────────────────────────────

[0204]

[Chemical formula 66]

[0205]

[Chemical formula 67]

[0206]

[Chemical 68]

[0207]

[Chemical 69]

Second Photosensitive Emulsion Layer A compound D was prepared by using the above emulsion E on the first photosensitive emulsion layer.
A second photosensitive emulsion layer having a silver content of 1.3 g / m ² and gelatin of 0.7 g / m ² was coated in the same manner as the first photosensitive emulsion layer except that was not added. Protective lower layer On this, a protective lower layer having the following composition is added with gelatin 0.55 g / m
^It was applied so as to be ² .

──────────────────────────────────── Protective lower layer ───────── ─────────────────────────── 1-Hydroxy-2-benzaldoxime 15 mg / m ² Compound E 80 mg / m ² Compound F 10 mg / m ² polyethyl acrylate latex (average particle size 0.05 μm) 0.28 g / m ² ─────────────────────────────── ──────

[0210]

[Chemical 70]

[0211]

[Chemical 71]

Protective Upper Layer Furthermore, a protective upper layer having the following composition was further coated with gelatin 0.95.
It was applied so as to be g / m ² .

──────────────────────────────────── Protective lower layer ───────── ─────────────────────────── Amorphous matting agent (silicon dioxide, average particle size 3.0 μm) 30 mg / m ² Spherical matting agent ( PMMA, average particle size 2.7 μm) 30 mg / m ² liquid paraffin gelatin dispersion 50 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² water-soluble dye (Compound G) 45 mg / m ² ─────────────────────────────────────

[0214]

[Chemical 72]

Support As a support, a biaxially stretched polyethylene terephthalate support (thickness 100 μm) coated with the first and second undercoat layers having the following composition was used.

Undercoat layer First layer 10% by weight of potassium hydroxide was added to the following components to adjust the pH.
The coating solution adjusted to 6 was dried at 180 ° C. for 2 minutes,
The coating was applied so that the dry film thickness was 0.9 μm.

──────────────────────────────────── Undercoat layer 1st layer ───── ─────────────────────────────── The following core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6- Hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Compound H 0.20 g Colloidal silica (Sunotex ZL: particle size 70 to 100 μm, manufactured by Nissan Chemical Industries, Ltd.) 0.12 g Water was added. 100g ─────────────────────────────────────

[0218]

[Chemical formula 73]

[0219]

[Chemical 74]

Undercoat Layer Second Layer The following coating solution was applied at a drying temperature of 170 ° C. for 2 minutes to give a dry film thickness of 0.1 μm.

──────────────────────────────────── Undercoat layer Second layer ───── ──────────────────────────────── Gelatin 1g Methylcellulose 0.05g Compound I 0.02g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound J 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added to 100 g ─────────────────────── ──────────────

[0222]

[Chemical 75]

[0223]

[Chemical 76]

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

──────────────────────────────────── Conductive layer ───────── ─────────────────────────── SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² gelatin (Ca 2+ content 3000 ppm) 77 mg / m ² Compound K 7 mg / m ² Sodium dodecylbenzene sulfonate 10 mg / m ² Dihexyl-α-sulfosuccinate sodium 40 mg / m ² Sodium polystyrene sulfonate 9 mg / m ² ───── ───────────────────────────────

[0226]

[Chemical 77]

──────────────────────────────────── Back layer ───────── ─────────────────────────── Gelatin (Ca ²⁺ content: 30 ppm) 2.82 g / m ² Polymethylmethacrylate fine particles (average particle size) Diameter 3.4 μm) 54 mg / m ² compound K 3 mg / m ² compound L 40 mg / m ² compound M 40 mg / m ² compound N 80 mg / m ² compound O 120 mg / m ² sodium dodecylbenzenesulfonate 75 mg / m ² dihexyl -Α-sulfosuccinate sodium 20 mg / m ² compound P 5 mg / m ² sodium sulfate 50 mg / m ² sodium acetate 85 mg / m ² 1,2-bis (vinylsulfonylacetamido) ethane 150 mg / m ² ─────── ─────────────────────────────

[0228]

[Chemical 78]

[0229]

[Chemical 79]

[0230]

[Chemical 80]

[0231]

[Chemical 81]

[0232]

[Chemical formula 82]

A coated sample 41 was prepared by the above method.
A coated sample 42 was obtained in the same manner as in Sample 1 except that Emulsion F was used instead of Emulsion D in the first photosensitive layer and Emulsion G was used instead of Emulsion E in the second photosensitive layer. A coated sample 43 was obtained in the same manner as in the sample 1 except that the emulsion H was used instead of the emulsion D in the first photosensitive layer and the emulsion I was used instead of the emulsion E in the second photosensitive layer.

The evaluation was performed by the following test method. Photograph characteristics are as follows: Bright Room Printer P-6 manufactured by Dainippon Screen Co., Ltd.
After exposure through an optical wedge at 27 FM, an FG-680A automatic processor (Fuji Photo Film Co., Ltd.) was used with the developer having the following formulation.
Is a result of performing a treatment at 38 ° C. for 20 seconds. The fixing was carried out by a usual method (fixing solution: GR-F1). The practical sensitivity is the original consisting of halftone dots and fine lines (Japanese Patent Laid-Open No. 58-19
50% with the above printer using 0943 No. 1)
The value of Sample 41 was set to 100, which is the relative value of the reciprocal of the appropriate exposure amount so that the dot area of 50% of each sample area becomes 50%. The practical skill Dmax is the maximum blackening density when the appropriate exposure amount is given. The processing is similar to the above. The gradation is a relative value of the slope of the characteristic curve, and the value of the sample 41 is set to 100. The larger the value, the harder the image. The processing is similar to the above.

In the test for the image quality of blank characters, an original consisting of halftone dots and fine lines (FIG. 1 of JP-A-58-190943) was used and exposed with the printer. The processing is similar to that for photographic properties. Here, the blank character image quality 5 means that a halftone dot area of 50% is 5 on the photosensitive material using a document as shown in FIG.
It refers to the image quality in which a character having a width of 30 μm is reproduced when properly exposed so that a halftone dot area is 0%, and it is a very good extracted character image quality. On the other hand, the blank character image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same proper exposure is given, and is a defective blank character image quality. A rank of ~ 2 has been set. A level of 3 or more is a practical level.

The composition of the developing solution is shown below. ──────────────────────────────────── Developer ──────────── ──────────────────────── Potassium hydroxide 35.0 g Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Bromide Potassium 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2 -Thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.15 g sodium erythorbate 3.0 g Water was added 1 liter Potassium hydroxide was added pH = 10.5 ────────────────────────────────────

The above results are shown in Table 6.

[0238]

[Table 6] Table 6 ──────────────────────────────────── Sample dopant Sensitivity Dmax Without gradation Character image quality 41 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 100 5.2 100 3 42 K ₃ [Cr (CN) ₆ ] 115 5.4 91 4 43 K ₃ [Cr (CN) ₆ ] * 99 5.3 105 5 ──────────────────────────────────── (Note) K ₃ [Cr ( CN) ₆ ] *: Used in a relatively large amount

[Example 5] (Preparation of emulsion J) 32 g of lime-processed gelatin was added to 80 g of distilled water.
After adding to 0 ml and melt | dissolving at 40 degreeC, 5.76 g of sodium chloride was added, and the temperature was raised to 55 degreeC. To this solution, 1.0 cc of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added. Then silver nitrate 1
A solution prepared by dissolving 00 g in 400 ml of distilled water and a solution prepared by dissolving 34.4 g of sodium chloride in 400 ml of distilled water were mixed with each other.
While maintaining the temperature at 5 ° C, the above liquid was added and mixed over 35 minutes. Next, a solution prepared by dissolving 59.2 g of silver nitrate in 200 ml of distilled water and a solution prepared by dissolving 17.1 g of sodium chloride in 200 ml of distilled water were added and mixed for 18 minutes while maintaining the temperature at 55 ° C. After cooling to 40 ° C., the following red-sensitizing sensitizing dye was added in an amount of 4 × 10 ⁻⁵ mol per mol of silver halide, and then a solution prepared by dissolving 0.8 g of silver nitrate in 100 ml of distilled water and potassium bromide were added. A solution prepared by dissolving 0.56 g in 100 ml of distilled water was added and mixed for 10 minutes while maintaining 40 ° C. After desalting and washing with water, 90 g of lime-processed gelatin was added, and pAg was adjusted to 7.3 and pH was adjusted to 6.2 with sodium chloride and sodium hydroxide.
After the temperature was raised to 50 ° C., optimal gold sulfur sensitization was performed. The silver chlorobromide emulsion thus obtained (silver bromide 0.5 mol%
Was included in Emulsion J.

(Preparation of Emulsion K) Emulsion J means 1 × 10 ⁻⁸ mol of K ₃ [RhC per mol of finished silver chlorobromide]
1 ₆ ] was added in the same manner except that the sodium chloride solution added for the second time was added to prepare a silver chlorobromide emulsion.

With respect to Emulsion K, silver chlorobromide emulsions L to S were prepared in the same manner except that the kind and amount of the metal complex added to the sodium chloride solution added the second time were changed according to Table 7.

With respect to the emulsions J to S thus prepared, the particle shape, particle size, and particle size distribution were determined from electron micrographs. The particle size is represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size. Emulsions J to S all have a grain size of 0.4
It was a cubic particle having a particle size distribution of 0.09 and a size of 5 μm.

(Preparation of Photosensitive Material 101) After corona discharge treatment was applied to the surface of a paper support laminated with polyethylene on both sides, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were applied. Then, a multi-layer color photographic paper (101) having the following layer constitution was produced.

Preparation of Third Layer Coating Liquid Magenta coupler (ExM) 40.0 g, ultraviolet absorber (UV-2) 40.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-5) 25.0 g, color image stabilizer (Cpd-6) 2.5 g, color image stabilizer (Cpd-)
7) 20.0 g, color image stabilizer (Cpd-8) 2.5 g,
5.0 g of a color image stabilizer (Cpd-10) was added to a solvent (Sol
v-3) 32.5 g, solvent (Solv-4) 97.5
g, solvent (Solv-6) 65.0 g and ethyl acetate 1
This was dissolved in 10 ml, and this solution was emulsified and dispersed in 1500 g of a 7% gelatin aqueous solution containing 90 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion (cube, average grain size of 0.
A 1: 3 mixture of 55 μm large size emulsion and 0.39 μm small size emulsion (silver molar ratio). The variation coefficients of the grain size distribution were 0.08 and 0.06, respectively, and in each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. 0.1 mg of potassium hexachloroiridium (IV) in total and 1.0 mg of potassium ferrocyanide in total were contained in the inside of the grain and in the silver bromide localized phase per 1 mol of silver. ) Was prepared. In this emulsion, the green sensitizing dyes D, E and F shown below were added to large size emulsions at 3.0 × 10 -4 and 4.0 / mol of silver, respectively.
X 10 ^-5 mol and 2.0 X 10 -4 were added to each of the small size emulsions to give 3.6 x 10 -4 and 7.0 x 10 per mol of silver.
After the addition of ^-5 mol and 2.8 × 10 -4, a sulfur sensitizer and a gold sensitizer were added in the presence of a decomposed product of nucleic acid to perform optimum chemical sensitization. The above emulsified dispersion A and this silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the third layer having the composition shown below.

Other coating solutions for the first to seventh layers were prepared in the same manner as the coating solution for the third layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Moreover, Cpd-12 is added to each layer.
And Cpd-13 are 25.0 mg / m ² and 5 respectively.
The amount added was 0.0 mg / m ² . The following were used as the spectral sensitizing dyes of the silver chlorobromide emulsion in each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0246]

[Chemical 83]

[0247]

[Chemical 84]

[0248]

[Chemical 85]

(1.4 × 10 ^-4 mol for each large-sized emulsion and 1.7 × 10 ^-4 mol for each small-sized emulsion) per mol of silver halide. ) Green-sensitive emulsion layer

[0250]

[Chemical 86]

[0251]

[Chemical 87]

[0252]

[Chemical 88]

(The sensitizing dye D is based on 1 mol of silver halide,
3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, sensitizing dye E is large size emulsion per mol of silver halide To 4.0 × 10 ⁻⁵ mol, and for small size emulsions, 7.0 × 10 ⁻⁵ mol, sensitizing dye F is silver halide 1
2.0 × 10 ⁻⁴ mol was added to the large size emulsion and 2.8 × 10 ⁻⁴ mol was added to the small size emulsion per mol. ) Red-sensitive emulsion layer

[0254]

[Chemical 89]

(Sensitizing dye G was added per mol of silver halide,
4.0 × 10 ⁻⁵ mol was added. Further, the following compounds were added to the red-sensitive silver halide emulsion in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0256]

[Chemical 90]

Further, 1 × (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, at 8.5 × per mol of silver halide. 10 ^-4 , 3.0 x 10 ^-3 ,
2.5 × 10 ⁻⁴ mol was added. Further to the blue-sensitive emulsion layer and green-sensitive emulsion layer, K ₃ "Cr (CN) _6] respectively per mol of silver halide, 1 × 10 ^-4, were added 2 × 10 ^-4 mol.

Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer. Further, the coating pH was adjusted to be 5.9.

[0259]

[Chemical Formula 91]

[0260]

[Chemical Formula 92]

[0261]

[Chemical formula 93]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). However, for silver halide emulsions, the coating amount in terms of silver is shown.

Support (A) The resin layer on the first layer side contains a bluish dye (ultraviolet).

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 5: 5 mixture of large size emulsion having average grain size of 0.88 μm and small size emulsion of 0.70 μm (silver molar ratio)). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. And 0.1 mg of potassium hexachloroiridium (IV) in total per mol of silver in the silver bromide localized phase, and 1.0 mg of potassium ferrocyanide in total) 0.27 gelatin 1.22 yellow coupler ( ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.01 solvent (Solv-1 0.13 solvent (Solv-5) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 0.90 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 solvent (Solv-8) 0.03

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (silver molar ratio)). The coefficient of variation of the grain size distribution was 0.08 and 0.06, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. And 0.1 mg of potassium hexachloroiridium (IV) in total and 1.0 mg of potassium ferrocyanide in total in the silver bromide localized phase per 1 mol of silver) 0.13 gelatin 1.45 magenta coupler ( ExM) 0.16 UV absorber (UV-2) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0 .01 color image stabilizer (Cpd 7) 0.08 color image stabilizer (Cpd-8) 0.01 color image stabilizer (Cpd-10) 0.02 solvent (Solv-3) 0.13 solvent (Solv-4) 0.39 solvent (Solv -6) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.68 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02

Fifth layer (red-sensitive emulsion layer) The silver chlorobromide emulsion A 0.18 gelatin 0.80 cyan coupler (ExC) 0.33 ultraviolet absorber (UV-2) 0.18 color image stabilizer ( Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-) 9) 0.02 color image stabilizer (Cpd-10) 0.01 solvent (Solv-1) 0.01 solvent (Solv-7) 0.22

Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05

Seventh layer (protective layer) Gelatin 0.90 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-11) 0.01

The compounds used are shown below.

[0272]

[Chemical 94]

[0273]

[Chemical 95]

[0274]

[Chemical 96]

[0275]

[Chemical 97]

[0276]

[Chemical 98]

[0277]

[Chemical 99]

[0278]

[Chemical 100]

[0279]

[Chemical 101]

[0280]

[Chemical 102]

[0281]

[Chemical 103]

[0282]

[Chemical 104]

[0283]

[Chemical 105]

[0284]

[Chemical formula 106]

[0285]

[Chemical formula 107]

[0286]

[Chemical 108]

[0287]

[Chemical 109]

[0288]

[Chemical 110]

[0289]

[Chemical 111]

[0290]

[Chemical 112]

[0291]

[Chemical 113]

[0292]

[Chemical 114]

[0293]

[Chemical 115]

[0294]

[Chemical formula 116]

[0295]

[Chemical 117]

[0296]

[Chemical 118]

[0297]

[Chemical formula 119]

[0298]

[Chemical 120]

Sample 101 was prepared as described above. Then, as shown in Table 7, Sample 1 was prepared in the same manner as Sample 101 except that the silver chlorobromide emulsion of the fourth layer (red-sensitive layer) was changed.
02-110 were produced.

In order to examine the tonality of the sample thus obtained, the sample was passed through an optical wedge and a red filter to give a value of 0.
After exposure for 1 second, color development processing was performed using the following processing steps and processing solutions. The optical density of this treated sample was measured to obtain a characteristic curve. As an index of toe gradation, the exposure amount and reflection density of 0.
The logarithmic difference ΔLogE of the exposure dose required to produce 5 was used. It is shown that the smaller the value of ΔLogE is, the more preferable gradation can be obtained in which a clear image with short legs and a lack of clearness can be obtained.

Safe light of the sample To check the safety, a 20 W light bulb and Fuji Photo Film 103A were used for the sample.
The sample was placed at a distance of 1 m from a safelight lamp consisting of two filters and one piece of paraffin paper, exposed to the safelight light for a predetermined time, and then exposed for 0.1 second through an optical wedge and a red filter. Color development processing was performed using the processing steps and processing solutions. The optical density of the treated sample irradiated with the safelight light and the treated sample not irradiated with the safelight light were measured to obtain a characteristic curve.
As an indicator of safelight safety, the safelight light irradiation time t required for the reflection density to reach 0.4 is used in the exposure amount required to bring the reflection density of the sample not irradiated with safelight light to 0.3. I was there. It is shown that the shorter the safelight light irradiation time t is, the less the concentration change due to the safelight light irradiation is caused, and the more excellent the safelight safety is.

To examine the raw preservation of the sample, 5 samples were taken.
After storing for 1 week in an atmosphere of 0 atmosphere, 0.1 second exposure was given through an optical wedge and a red filter, and color development processing was performed using the processing steps and processing solutions shown below. The optical densities of the treated samples of the sample stored for 1 week and the sample not stored under the atmosphere of 50 atm were measured to obtain characteristic curves. As an index of raw storability, the exposure amount required to bring the reflection density of an unsaved sample to 1.0 and 5
Reflection density of a sample stored for 1 week in an atmosphere of 0 atm.
The logarithmic difference ΔLogE of the exposure required to bring 0 was used. A positive value of ΔLogE indicates that the sensitivity increases with life time, and a negative value of ΔLogE indicates that the sensitivity decreases with life time. It shows that the smaller the absolute value of ΔLogE, the better the raw storage stability.

In order to examine the exposure humidity dependency of the sample, the sample was exposed for 0.1 second through an optical wedge and a red filter in an atmosphere of 25 ° C. 40% RH and 25 ° C. 85% RH, and the treatment shown below was performed. Color development processing was performed using the process and the processing solution. 25 ° C 40% RH and 25
The optical density of the treated sample exposed in the atmosphere of 85 ° C RH was measured to obtain a characteristic curve. As an index of exposure humidity dependency, the exposure amount required to bring the reflection density of 1.0 of a sample exposed in an atmosphere of 25 ° C. and 40% RH and 25 ° C. 85
The logarithmic difference ΔLogE of the exposure dose required to produce a reflection density of 1.0 for a sample exposed under an atmosphere of% RH was used.
When the value of ΔLogE is a positive value, it indicates that the sensitivity increases with exposure under high humidity, and when it has a negative value, the sensitivity decreases with exposure under high humidity. It is shown that the smaller the absolute value of ΔLogE, the better the exposure humidity dependency.

──────────────────────────────────── Treatment process Temperature Time Replenishment amount * Tank capacity ──────────────────────────────────── Color development 38.5 ℃ 45 seconds 73ml 500ml Bleach fixing 30〜 35 ° C 45 seconds Rinse 1 30-35 ° C 20 seconds Rinse 2 30-35 ° C 20 seconds Rinse 3 30-35 ° C 20 seconds Dry 70-80 ° C 60 seconds ────────────── ────────────────────── (Note) The replenishment amount * is the amount per 1 m ² of the light-sensitive material. The rinse was a three-tank countercurrent system from 3 to 1. The composition of each treatment liquid is as follows.

──────────────────────────────────── Color developer tank liquid replenisher ──── ──────────────────────────────── Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g potassium chloride 6.5 g None potassium bromide 0 0.03 g None Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonate ethyl) Hi Droxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 11.5 g Water was added to 1000 ml 1000 ml pH (25 ° C. ) 10.0 11.0 ────────────────────────────────────

──────────────────────────────────── Bleach-fix solution (tank solution and replenisher are the same ) ──────────────────────────────────── Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Water was added to 1000 ml pH (25 ° C.) (in acetic acid and ammonia water) 5.8 ──── ────────────────────────────────

As the rinse liquid, ion-exchanged water (calcium and magnesium were each 3 ppm or less) was used as both the tank liquid and the replenisher. The above results are shown in Table 7.

[0308]

[Table 7] Table 7 ──────────────────────────────────── Milk Dopant Sample Feet Safelight Life Insurance Exposure humidity agent Compound addition amount (mol / molAg) number Gradation Safety Existence Dependency ────────────────────────────── ────── J None 101 0.23 35 -0.05 -0.08 K K ₃ [RhCl ₆ ] 1 x 10 ^-8 102 0.21 22 -0.10 -0.07 L K ₃ [RhCl ₆ ] 2 x 10 ^-8 103 0.19 12- 0.14 -0.07 M K ₃ [RhCl ₆ ] 4 x 10 ^-8 104 0.17 7 -0.18 -0.06 NK ₂ [Ru (NO) Cl ₅ ] 1 x 10 ^-8 105 0.20 19 -0.09 -0.07 OK ₂ [Ru (NO) Cl ₅ ] 2 × 10 ^-8 106 0.18 12 -0.14 -0.06 PK ₂ [Ru (NO) Cl ₅ ] 4 × 10 ^-8 107 0.17 6 -0.17 -0.06 Q K ₃ [Cr (CN) ₆ ] 1 x 10 ^-8 108 0.21 33 -0.06 -0.04 RK ₃ [Cr (CN) ₆ ] 2 x 10 ^-8 109 0.19 30 -0.06 -0.03 SK ₃ [Cr (CN) ₆ ] 4 x 10 ^-8 110 0.18 28- 0.07 -0.03 ─────────────────────────────────────

[Example 8] (Preparation of emulsion T) 32 g of lime-treated gelatin was added to 80 g of distilled water.
After adding to 0 ml and dissolving at 40 ° C., 3.3 g of sodium chloride was added and the temperature was raised to 70 ° C. Subsequently, a solution prepared by dissolving 100 g of silver nitrate in 400 ml of distilled water and a solution prepared by dissolving 34.4 g of sodium chloride in 400 ml of distilled water were added to and mixed with the above solution over 43 minutes while maintaining 70 ° C. Next, 60.0 g of silver nitrate is added to 200 ml of distilled water.
And 20.6 g of sodium chloride and 1.0 × 10 ^-5 mol of K ₃ per mol of the finished silver chlorobromide.
A liquid obtained by dissolving [Fe (CN) ₆ ] in 200 ml of distilled water was added and mixed for 18 minutes while maintaining 70 ° C.
After the temperature was lowered to 40 ° C., desalting and washing with water were carried out, 90 g of lime-treated gelatin was added, and the temperature was raised to 50 ° C. Then, the red photosensitive sensitizing dye G used in Example 1 was added to 4 parts per mol of silver halide. X 10 ^-5 mol was added, and then K ₂ [IrCl corresponding to 1.2 × 10 ^-6 mol per mol of the finished silver chlorobromide was added.
₆ ] containing a silver bromide fine grain emulsion (average grain size 0.
05 μm) was added in such an amount that the silver bromide content became 1.0 mol%. Furthermore, it was optimally subjected to gold sulfur sensitization. The silver chlorobromide emulsion (containing 1.0 mol% of silver bromide) thus obtained was designated as Emulsion T.

(Preparation of Emulsion U) In preparation of Emulsion T,
A silver chlorobromide emulsion was prepared in the same manner by adding 1.5 × 10 ^-8 mol of K ₃ [RhCl ₆ ] per mol of the finished silver chlorobromide to the sodium chloride solution added for the second time. This was designated as Emulsion U.

(Preparation of emulsion U) In preparation of emulsion T,
A silver chlorobromide emulsion was prepared which was different only in that 1.5 × 10 ^-8 mol of K ₃ [Cr (CN) ₆ ] was added to the sodium chloride solution to be added a second time per mol of the finished silver chlorobromide. This was designated as Emulsion V.

With respect to the emulsions T to V thus prepared, the grain shape, grain size, and grain size distribution were determined from electron micrographs. The particle size is represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size. Emulsions T to V all have a grain size of 0.4
It was a cubic particle having a particle size distribution of 9 μm and a particle size distribution of 0.09. In addition, the X-ray diffraction of Emulsions T to V showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol% to 40 mol%.

In the preparation of Sample 101 of Example 7, 1- (5-methylureidophenyl) -5- which had been added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
Sample 201 was prepared in the same manner except that the mercaptotetrazole was removed and the emulsion of the red photosensitive emulsion layer was changed to emulsion K. In the preparation of Sample 201, the compounds shown in Table 8 were added to the red light-sensitive emulsion layer, the emulsion of the red light-sensitive emulsion layer was changed as shown in Table 8, and the coating pH was changed as shown in Table 8. Sample 202 to
209 was created.

The toe gradation, safelight safety, raw storability and exposure humidity dependency of the sample thus obtained were examined in the same manner as in Example 7. The results are shown in Table 8.

[0315]

[Table 8] Table 8 ──────────────────────────────────── Sample Red Photosensitive emulsion layer coating pH Foot Safelight Life Insurance Exposure Humidity Emulsion Additive * Gradation Safety Existence Dependency ─────────────────────────────── ───── 201 T None 5.9 0.23 35 -0.10 -0.08 202 T III-2-2 6.2 0.23 35 -0.05 -0.08 203 T IV-1 5.9 0.22 34 -0.06 -0.08 204 U None 6.0 0.19 13 -0.16- 0.08 205 U III-2-2 5.9 0.20 12 -0.14 -0.07 206 U IV-1 6.1 0.19 13 -0.13 -0.08 207 V None 6.0 0.19 30 -0.09 -0.05 208 V III-2-2 5.8 0.18 33 -0.06- 0.03 209 V IV-1 5.9 0.19 32 -0.07 -0.04 210 V IV-1 4.2 0.20 33 -0.09 -0.04 ────────────────────────── ─────────── (Note) Additive *: Addition amount 3 × 10 ^-4 mol per mol of silver halide in the red-sensitive emulsion layer

[Example 9] "Preparation of silver bromide cubic emulsion" To 870 ml of water, 36 g of deionized gelatin and 0.25 g of potassium bromide were added and dissolved. While stirring in this gelatin aqueous solution kept at 75 ° C, 0.088 M silver nitrate aqueous solution (solution 15) 36 m
1 and 0.088M potassium bromide aqueous solution (solution 16) 36
A fixed amount of 10 ml was added by the double jet method for 10 minutes, and subsequently, 176 ml of each of Solution 15 and Solution 16 was added by the double jet method for 7 minutes. Then, 1010 ml of 0.82 M silver nitrate aqueous solution (solution 17) was initially added at 1.8 ml / min.
Was added for 78 minutes by accelerating the flow rate from the flow rate of (1), and at the same time, a 0.90 M potassium bromide aqueous solution (solution 18) was added while controlling so as to keep the silver potential +100 mV (vs. saturated calomel electrode). After 5 minutes from the completion of the addition, the temperature was lowered to 35 ° C., soluble salts were removed by an ordinary sedimentation method, and then the temperature was raised to 40 ° C. again, and 50 g gelatin was added and dissolved.
Further, sodium chloride and phenol were added to adjust the pH to 6.
Adjusted to 5. The obtained particles have a side length of 0.65
It was a monodisperse silver bromide cube with a size of 10%.

“(NH ₄ ) ₂ [RhCl ₅ (H ₂ O)]
Preparation of Silver Bromide Cubic Emulsion Doped with. In the preparation of the above emulsion, solution 18 was 1 × 10 ⁻⁸ , 1 × 10 ⁻⁷ and 1 × 10 ⁻⁶ mol (N) per mol of silver added, respectively.
Emulsions were prepared in the same manner except that H ₄ ) ₂ [RhCl ₅ (H ₂ O)] was added.

[0318] _{"K 3 [Cr (CN) 6} ] Preparation of doped silver bromide cubic emulsion" in the preparation of the emulsion, solution 18, silver, respectively per mol 1 × 10 ^-8 to be added,
1 × 10 ⁻⁷ and 1 × 10 ⁻⁶ mol of K ₃ [Cr (CN)]
_The emulsions were prepared in the same manner except that [ ₆ ] was included.

These emulsions were coated in the same manner as in Example 1 to obtain coated samples. After these samples were exposed to sensitometry (1 second) through a BPN-42 filter (blocking light of 420 nm or more) through an optical wedge,
After development with a MAA-1 developing solution at 20 ° C. for 10 minutes, it was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured. Fog was determined by the minimum optical density of the sample. The sensitivity is
It was expressed by the reciprocal of the exposure amount required to obtain the optical density of fog + 0.5, and was expressed as a relative value with the value of Sample 201 being 100. The gradation represents the slope of the characteristic curve portion, and the larger the gradation, the harder the gradation. The foot density represents the optical density obtained by subtracting the minimum optical density from the optical density when an exposure amount 0.8 times the exposure amount giving the above sensitivity is given, and the lower the value, the more the characteristic curve is cut off. Indicates. The results are shown in Table 9.

[0320]

[Table 9] Table 9 ──────────────────────────────────── Sample dopant fog Sensitivity Gradation Concentration number Compound amount ──────────────────────────────────── 201 None 0.07 100 2.2 0.35 202 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ⁻⁸ 0.06 67 2.1 0.28 203 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-7 0.06 23 3.0 0.28 204 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-6 0.05 7 3.9 0.25 205 K ₃ [Cr (CN ) ₆ ] 1 x 10 ^-8 0.06 80 2.3 0.34 206 K ₃ [Cr (CN) ₆ ] 1 x 10 ^-7 0.05 57 57 2.6 0.27 207 K ₃ [Cr (CN ) ₆ ] 1 × 10 ^-6 0.05 5.7 0.19 ───────────────────────────────── ───

[Example 10] Sample Nos. 201 and 2 above
The emulsions used to prepare 03, 204, 206 and 207 contained 9.2 x 10 ^-6 mol sodium thiosulfate, 2.1 x 10 ^-6 mol potassium chloroaurate and 2.5 x mol per mol silver. Optimum chemical sensitization was carried out at 60 ° C. by adding 10 ⁻⁴ mol of potassium thiocyanate. . After that, coating was performed in the same manner as above to obtain coated samples 301 to 305, respectively.

These samples were exposed to sensitometry (1 second) through a BPN-42 filter (blocking light of 420 nm or more) through an optical wedge, and then exposed with the above-prepared MAA-1 developer at 20. After developing at 10 ° C. for 10 minutes, stopping, fixing, washing with water and drying were carried out by a conventional method, and the optical density was measured. Fog was determined by the minimum optical density of the sample. The sensitivity was represented by the reciprocal of the exposure amount required to obtain an optical density of fog + 0.5, and was represented as a relative value with the value of Sample 301 being 100. The gradation represents the slope of the characteristic curve portion, and the larger the gradation, the harder the gradation. The foot density represents the optical density obtained by subtracting the minimum optical density from the optical density when an exposure amount 0.8 times the exposure amount giving the above sensitivity is given, and the lower the value, the more the characteristic curve is cut off. Indicates. The results are shown in Table 10.

[0323]

[Table 10] Table 10 ──────────────────────────────────── Sample dopant fog Sensitivity Gradation Concentration number Compound addition amount ───────────────────────────────────── 8 None 0.10 100 2.2 0.36 9 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ⁻⁷ 0.08 40 2.6 0.32 10 (NH ₄ ) ₂ [RhCl ₅ (H ₂ O)] 1 × 10 ^-6 0.09 5 3.7 0.23 11 K ₃ [Cr (CN) ₆ ] 1x 10 ^-7 0.07 64 4.0 0.25 12 K ₃ [Cr (CN) ₆ ] 1x 10 ^-6 0.05 9 6.4 0.15 ─────────────────────────────────────

Example 11 [K ₃ [Fe (CN) ₆ ], K ₃ [Ru (CN) ₆ ],
K ₃ [Co (CN) ₆ ] or K ₃ [Ir (CN) ₆ ]
Preparation of Silver Bromide Cubic Emulsion Doped with "In Preparation of Emulsion A of Example 1, 1 × 10 ^-6 per mol of silver halide
Mol of K ₃ [Fe (CN) ₆ ], K ₃ [Ru (CN)]
₆ ], K ₃ [Co (CN) ₆ ] or K ₃ [Ir (C
N) ₆ ] was added to Solution 4 to prepare a silver halide emulsion in the same manner. A sample was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 11. In Table 11, the results of the undoped sample and the sample doped with K ₃ [Cr (CN) ₆ ] are also reproduced for reference.

[0325]

[Table 11] Table 11 ──────────────────────────────────── Dopant fog sensitivity Gradation Toe density ──────────────────────────────────── None 0.06 100 2.6 0.32 K ₃ [ Cr (CN) ₆ ] 0.05 10 5.7 0.07 K ₃ [Fe (CN) ₆ ] 0.05 99 2.8 0.31 K ₃ [Ru (CN) ₆ ] 0.05 97 2. 7 0.30 K ₃ [Co (CN) ₆ ] 0.05 95 95 2.5 0.32 K ₃ [Ir (CN) ₆ ] 0.05 101 2.6 0.33 ───────── ────────────────────────────

Example 12 To each emulsion prepared in Example 11, 1 × 10 ⁻² mol of silver bromide fine grain emulsion, 2.5 × 10 ⁻⁶ mol of sodium thiosulfate and 3 mol of silver per mol of silver were added.
Optimal chemical sensitization was performed at 60 ° C. by adding × 10 ⁻⁷ mol of chloroauric acid. A sample was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 12. In Table 12, the results of the undoped sample and the sample doped with K ₃ [Cr (CN) ₆ ] are also reproduced for reference.

[0327]

[Table 12] Table 12 ──────────────────────────────────── Dopant fog sensitivity Gradation Toe density ──────────────────────────────────── None 0.10 100 2.2 0.36 K ₃ [ Cr (CN) ₆ ] 0.05 9 6.4 0.15 K ₃ [Fe (CN) ₆ ] 0.14 50 2.4 0.35 K ₃ [Ru (CN) ₆ ] 0.05 52 2. 3 0.37 K ₃ [Co (CN) ₆ ] 0.05 73 2.2 0.33 K ₃ [Ir (CN) ₆ ] 0.05 75 75 2.4 0.36 ───────── ────────────────────────────

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/00 530

Claims (1)

[Claims] 1. A surface latent image type silver halide photographic light-sensitive material having at least one surface latent image type silver halide emulsion layer on a support, wherein the surface latent image type silver halide grains of the emulsion layer are A surface latent image type silver halide photographic light-sensitive material containing a cyanochrome complex ion represented by the following formula (I). (I) [Cr (CN) _6-n L _n ] ^m -wherein L is H ₂ O or OH, n is 0 or 1, and m is 3 or 4.