JPH06214336A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material high in sensitivity and small in gradation change with the lapse of time by incorporating seleniumsensitized silver halide grains and a specified sensitizing dye in an emulsion layer. CONSTITUTION:The silver halide emulsion layer contains the seleniumsensitized silver halide grains and at least each one of trimethine cyanine dyes and monomethine cyanine dyes, preferably, represented by formula I and formula II, respectively, in which each of Z<1> and Z<2> is an atomic group necessary to form a ring, such as a benzimidazole ring; each of Z<3> and Z<4> is an atomic group necessary to form a ring, such as a pyrroline ring; each of R<1> and R<2> is an aliphatic hydrocarbon group; each of R<3> and R<4> is an aliphatic group; R<0> is H, alkyl, or aralkyl; each of X(1) and X(2) is an acid anion; and each of m and n is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity and excellent latent image storability.

[0002]

2. Description of the Related Art The technical progress of silver halide color light-sensitive materials for photography (including color negatives and color reversal light-sensitive materials; hereinafter simply referred to as "color negatives") has continued unabated, and it has been possible to obtain conventional high-sensitivity films. The so-called ISO sensitivity 400 class light-sensitive material has been used as a regular film for general users.

Along with this, many studies have been conducted to achieve high sensitivity and high image quality.

For example, a chemical sensitization method is one of the studies, and as a typical method, sulfur sensitization, selenium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization and a combination thereof are used. Various sensitization methods are known.

Of these, selenium sensitization is one of the chemical sensitization methods that has been attracting attention because of its great sensitizing effect, but it is disadvantageous in that it causes a large amount of fog and is soft.
Several improvements have been made for this improvement. For example,
JP-B-44-15748 discloses a method of chemically sensitizing with at least two different sensitizers of a noble metal sensitizer and an unstable selenium sensitizer, and JP-B-43-13489 describes a noble metal sensitizer. A method of chemically sensitizing an unstable selenium sensitizer and an unstable sulfur sensitizer with three different sensitizers is disclosed.

On the other hand, regarding the spectral sensitization method, for example, regarding chemical sensitization in the presence of a spectral sensitizing dye,
US Pat. Nos. 4,183,756 and 4,225,66
No. 6, a technique for adding a sensitizing dye during the silver halide grain forming step, and JP-A Nos. 58-7629, 59-9658, 59-48756 and 59-1.
The technique of adding a sensitizing dye to an emulsion before or during the chemical sensitization disclosed in No. 13920 can be mentioned.

Further, from the viewpoint of particle shape, Japanese Patent Laid-Open No.
8-113930, 58-113934, 59
No. 119350, and each publication discloses a multi-layer structure in which a tabular silver halide emulsion having an aspect ratio of 8 or more is used in a high-sensitivity layer and which has high sensitivity and improved graininess, sharpness and color reproducibility. A color photographic light-sensitive material is disclosed. One of the advantages of flat-plate silver halide emulsions is that the specific surface of silver halide per unit volume can be increased so that a large amount of sensitizing dye can be added and light absorption can be increased, resulting in high sensitivity without impairing graininess. May become possible.

On the basis of these findings, the present inventor has attempted to perform selenium sensitization mainly on a tabular silver halide emulsion in the presence of a spectral sensitizing dye, aiming at higher sensitivity. . However, while conducting many evaluations for commercialization of this selenium-sensitized tabular emulsion, in addition to the increase in fog immediately after production, it is possible that the contrast increases after photographing (so-called latent image aging). We came to recognize that it was a big problem.

Therefore, in the conventional technology, it is not possible at the same time to achieve both high sensitivity and prevention of high contrast due to latent image aging, and there has been a long-awaited solution to this problem.

[0010]

As can be seen from the above, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and having little change in gradation with the passage of latent image.

[0011]

As a result of intensive studies to achieve the above-mentioned object, the present inventor has confirmed that the above-mentioned object can be achieved by the following silver halide photographic light-sensitive material.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, silver halide grains in the emulsion layer are selenium-sensitized, and in the emulsion layer At least one trimethine cyanine dye and at least one monomethine cyanine dye
A silver halide photographic light-sensitive material characterized by containing one of the following.

(2) The silver halide grains selenium-sensitized in the presence of at least one trimethine cyanine dye and at least one monomethine cyanine dye, as described in the above item (1). Silver halide photographic light-sensitive material.

(3) The silver halide photographic light-sensitive material described in (1) or (2) above, which contains an emulsion containing silver halide grains having an average aspect ratio of 3 or more.

The present invention resides in that the selenium-sensitized emulsion is used in combination with two kinds of sensitizing dyes, monomethine and trimethine. By this combination, silver halide having high sensitivity and little change in gradation over time of latent image is obtained. You can get photo tourism materials for the first time. Several attempts have been made to combine the use of monomethine and trimethine dyes, for example, JP-A-2-167039.
Although it is described in JP-A-4-152336 and the like, there is no description about the relation with selenium sensitization, and this effect was an unexpected discovery.

The contents of the present invention will be described in detail below.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in various documents can be used. That is, it is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound,
For example, JP-B-44-15748 and JP-B-43-13
No. 489, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22
It is preferable to use the compounds described in No. 9300. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3
-Chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides,
Colloidal metal selenium may be mentioned.

Although the preferred types of labile selenium compounds have been described above, these are not limiting. To those skilled in the art, when it comes to unstable selenium compounds as sensitizers for photographic emulsions, the structure of the compounds is not so important as long as selenium is unstable. It is generally understood that the organic moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, JP-B-46-4553 and JP-B-52-3 are known.
The compounds described in JP-B-4492 and JP-B-52-34491 are used. Specific examples of the non-unstable selenium compound include selenious acid, potassium selenocyanide,
Examples thereof include selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethiones and derivatives thereof.

Among these selenium compounds, compounds represented by the following general formula (A) and compounds represented by the general formula (B) can be mentioned.

[0021]

[Chemical 1] In the formula, Z ₁ and Z ₂ may be the same or different, and are each an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl), an aralkyl group. (Eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg, pyridyl, thienyl). , Furyl, imidazolyl), -NR ₁ (R
₂₎ - represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ .

However, R ₁ and R ₂ are hydrogen or an acyl group (eg, acetyl, propanoyl, benzoyl,
Heptafluorobronoyl, difluoroacetyl, 4-
Nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl).

In the general formula (A), Z ₁ preferably represents an alkyl group, an aryl group or --NR ₁ (R ₂ ) and Z ₂
Represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R
₆ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, or an acyl group.

Of the selenium compounds represented by the general formula (A), more preferably N, N-dialkylselenourea,
N, N, N'-trialkyl-N'-acyl selenoureas, tetraalkyl selenoureas, N, N-dialkyl-
Aryl selenamide, N-alkyl-N-aryl-
It is an aryl selenoamide.

[0026]

[Chemical 2] In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group or -OR.
_{7, -NR 8 (R 9)} , - SR 10, -SeR 11, X, represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom and X represents a halogen atom.

In the general formula (B), Z ₃ , Z ₄ ,
When Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are aliphatic groups, specific examples thereof include linear, branched or cyclic alkyl groups, alkenyl groups, alkynyl groups and aralkyl groups ( For example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-
Decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (B), Z ₃ , Z ₄ ,
When Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are aromatic groups, specific examples thereof include a monocyclic or condensed ring aryl group (eg, phenyl, pentafluorophenyl,
4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (B), Z ₃ , Z ₄ ,
When Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are heterocyclic groups, specific examples thereof are 3 to 10-membered containing at least one of nitrogen atom, oxygen atom or sulfur atom. A ring saturated or unsaturated heterocyclic group (eg, pyridyl,
Thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In the general formula (B), when R ₇ , R ₁₀ and R ₁₁ are cations, specific examples thereof include an alkali metal atom or ammonium, and when X is a halogen atom, specific examples thereof. Examples include fluorine, chlorine, bromine or iodine.

In the general formula (B), Z ₃ , Z ₄ or Z ₅ preferably represents an aliphatic group, an aromatic group or --OR ₇ ,
R ₇ represents an aliphatic group or an aromatic group.

Among the selenium compounds represented by the general formula (B), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate are more preferable.

Specific examples of the compounds represented by the general formulas (A) and (B) are shown in the following chemical formulas 3 to 10, but the selenium sensitizer used in the present invention is not limited thereto. Absent.

[0035]

[Chemical 3]

[0036]

[Chemical 4]

[0037]

[Chemical 5]

[0038]

[Chemical 6]

[0039]

[Chemical 7]

[0040]

[Chemical 8]

[0041]

[Chemical 9]

[0042]

[Chemical 10] These selenium sensitizers include, for example, water or methanol,
Dissolved in an organic solvent such as ethanol alone or in a mixed solvent, or Japanese Patent Application Nos. 2-264447 and 2-26.
No. 4448 is added at the time of chemical sensitization of emulsion. It is preferably added before the start of chemical sensitization of the emulsion. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, and preferably, The amount is 1 × 10 ^-8 mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more 1 ×
It is 10 ^-5 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and p
H is arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

The selenium sensitization is more effective in the presence of a silver halide solvent.

The silver halide solvent which can be used for selenium sensitization in the present invention is, for example, US Pat.
71,157, 3,531,289, 3,
574, 628, JP-A-54-1019, 54-
(A) Organic thioethers described in JP-A-158917, JP-A-53-82408 and JP-A-55-77737.
(B) thiourea derivatives described in JP-A No. 55-2982 and (c) described in JP-A-53-144319.
Silver halide solvent having a thiocarbonyl group sandwiched between oxygen or sulfur and nitrogen, JP-A-54-100717
(D) imidazoles, (e) sulfite, and (f) thiocyanate.

Among the solvents used for the selenium sensitization, particularly preferable solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

The silver halide photographic emulsion used in the light-sensitive material of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization.

Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples thereof include thiosulfates, thioureas, allyl isothiocyanates, cystines, p-toluene thiosulfonates, and rhodanines. In addition, for example, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313,
No. 3,656,955, German patents 1,4
No. 22,869, Japanese Patent Publication No. 56-24937, Japanese Patent Laid-Open No. 5
The sulfur sensitizer described in JP-A-5-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount is
It varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but is not less than 1 × 10 ⁻⁷ mol and not more than 5 × 10 ⁻⁴ mol per mol of silver halide. preferable.

As the gold sensitizer in the above gold sensitization,
The oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Typical examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate and pyridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 per mol of silver halide.
It is preferably not less than 5 and not more than 5 × 10 ⁻⁴ mol.

In the chemical ripening, there is no particular limitation on the timing and order of addition of the silver halide solvent and the selenium sensitizer, or the sulfur sensitizer and / or the gold sensitizer which can be used in combination with the selenium sensitizer. It is not necessary to provide it, and the above compounds can be added at the same time, or at different addition points, during the initial (preferably) or during the progress of chemical ripening. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone and added.

The preferred trimethine cyanine dye used in the present invention is represented by the following general formula (I).

[0055]

[Chemical 11] In formula (I), Z ¹ and Z ² are benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, or naphthoselenazole. Represents a group of atoms necessary to form a nucleus. The naphthoxazole nucleus, naphthothiazole nucleus and naphthoselenazole nucleus are naphtho [1,2-
d] oxazole nucleus, naphtho [2,1-d] oxazole nucleus, naphtho [1,2-d] thiazole nucleus, naphtho [2,1-d] thiazole nucleus, naphtho [2,3-d] thiazole nucleus, naphtho It includes a [1,2-d] selenazole nucleus and a naphtho [2,1-d] selenazole nucleus.

The aromatic ring contained in these nuclei may have various substituents. For example, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group having up to 6 carbon atoms (eg, methyl group, ethyl group, isopropyl group, 3-propyl group, butyl group, t-amyl group),
Cyano group, carboxy group, alkoxycarbonyl group having up to 4 carbon atoms (eg ethoxycarbonyl group), alkylcarbonyl group having up to 4 carbon atoms (eg acetyl group), alkylsulfonyl group having 4 or less carbon atoms (eg methylsulfonyl group), Aromatic hydrocarbon group (eg phenyl group, p-tolyl group), halogen-substituted alkyl group (eg trifluoromethyl group), hydroxy group, alkoxy group having up to 4 carbon atoms (eg methoxy group, ethoxy group), or carbon number It may have up to 4 alkylcarbonylamino groups (eg acetylamino groups) and the like. On the 1-position nitrogen atom of the benzimidazole nucleus, an alkyl group having up to 4 carbon atoms (eg, methyl group, ethyl group, propyl group), an alkenyl group having up to 4 carbon atoms (eg, allyl group), or an aromatic hydrocarbon group (For example, a phenyl group) and the like.

R ¹ and R ² represent an aliphatic hydrocarbon group having up to 8 carbon atoms which may be substituted and whose carbon chain may be interrupted by an oxygen atom, a sulfur atom or the like.

R ⁰ represents a hydrogen atom, an alkyl group having up to 3 carbon atoms (methyl group, ethyl group, propyl group, etc.) or an aralkyl group having up to 8 carbon atoms (eg, phenethyl group). X ₍₁₎ ^- represents an acid anion, m represents 1 or 2. However, m is 1 when the dye forms an inner salt.

Preferred monomethinecyanine dyes used in the present invention are represented by the following general formula (II).

[0060]

[Chemical 12] In the formula, Z ³ and Z ⁴ are a pyrroline nucleus, a pyridine nucleus, a thiazoline nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an indolenine nucleus, a benzimidazole nucleus, a benzoxazole nucleus, a benzthiazole nucleus, a benzselenazole nucleus, and a naphthoxazole, respectively. Represents a group of atoms necessary to complete a nucleus, a naphthothiazole nucleus, or a naphthoselenazole nucleus. The naphthooxazole nucleus includes a naphtho [1,2-d] oxazole nucleus and a naphtho [2,1
-D] oxazole nucleus, naphtho [1,2-d] thiazole nucleus and naphtho [2,1-d] for naphthothiazole nucleus.
A thiazole nucleus and a naphtho [2,3-d] thiazole nucleus are included, and a naphthoselenazole nucleus includes a naphtho [1,2-d] selenazole nucleus and a naphtho [2,1-d] selenazole nucleus. Various substituents may be present on the aromatic hydrocarbon ring of these nuclei, and those substituents may have the same substituents as those on the aromatic hydrocarbon ring in the case of Z ¹ and Z ² . You can use one. On the 3-position carbon atom of the indolenine nucleus, a lower alkyl group having up to 3 carbon atoms (for example, methyl group) can be possessed as a substituent.

At least one of R ³ and R ⁴ represents an aliphatic group having up to 8 carbon atoms, which is substituted with either a hydroxy group, a carboxy group, or a sulfo group, and the rest is a fatty acid group having up to 8 carbon atoms. Indicates a group. These aliphatic groups may further have another substituent (for example, a hydroxy group),
It may also be an aliphatic group whose carbon chain is interrupted by an oxygen atom or a sulfur atom.

[0062] X ₍₂₎ ^- represents an acid anion, n represents 1 or 2. N is 1 when the dye forms an inner salt.

Specific examples of the heterocyclic nuclei completed by Z ¹ or Z ² in the sensitizing dyes having the general formulas (I) and (II) used in the present invention are as follows. That is, 1-methyl-5-chlorobenzimidazole, 1-
Methyl-5-fluorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-methyl-
5,6-Difluorobenzimidazole, 1-ethyl-
5-chlorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-propyl-5-chlorobenzimidazole, 1-propyl-5-fluorobenzimidazole, 1-propyl-5,6-dichlorobenzimidazole, 1-propyl-5,6-difluorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-allyl -5,6-Dichlorobenzimidazole, 1-allyl-5,6-difluorobenzimidazole, 1-ethyl-5-methoxycarbonylbenzimidazole, 1-ethyl-5-methylsulfonylbenzimidazole, 1-phenyl-5-chloro Benzimidazole 1-phenyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-phenyl-5,6-difluorobenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole: oxazole, 4- Methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, 4-p-tolyloxazole, benzoxazole, 5-fluorobenzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole , 5-
Methylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6-di-
Methoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole, 5-acetylbenzoxazole, 5-hydroxybenzoxazole: naphtho [1,2-d] oxazole: thiazole,
4-methylthiazole, 4-phenylthiazole, 4,
5-dimethylthiazole, 4-methyl-5-phenylthiazole, benzthiazole, 5-chlorobenzthiazole, 5-bromobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-ethoxybenzothiazole, 6-methyl Benzthiazole,
6-chlorobenzothiazole, 5-carboxybenzothiazole, 5-acetylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-trifluoromethylbenzothiazole, 5-cyanobenzothiazole, 5,6-dimethyl Benzothiazole, 5-acetylaminobenzothiazole, 6-methoxybenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dichlorobenzothiazole, naphtho [1,2-d] thiazole, selenazole,
4-methylselenazole, 4-phenylselenazole,
4,5-dimethylselenazole, benzoselenazole,
With cores such as 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, and naphtho [1,2-d] selenazole. is there.

Specific examples of the heterocyclic nucleus completed by Z ³ or Z ⁴ include, in addition to the above, pyrroline, thiazoline, pyridine, 3,3-dimethylindolenine, 3,
3,6-trimethylindolenine, 6-chloro-3,3
Examples include nuclei such as dimethylindolenine and 3,3,5,6-tetramethylindolenine.

In the above general formulas (I) and (II), R
Specific examples of the substituents represented by ¹ , R ² , R ³ and R ⁴ are as follows. That is, methyl group, ethyl group, propyl group, butyl group, 2-methoxyethyl group, 2
-Ethylthioethyl group, 2-hydroxyethyl group, 3-
Hydroxypropyl group, 4-hydroxybutyl group, 2-
Carboxyethyl group, 3-carboxypropyl group, 4-
Carboxybutyl group, 3-carboxybutyl group, 2 (2
-Carboxyethoxy) ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Examples thereof include a sulfobutyl group, a 2- (3-sulfopropoxy) ethyl group, a 2-hydroxy-3-sulfopropyl group, a 3-sulfopropoxyethoxyethyl group, and a vinylmethyl group. X ₍₁₎ ^- and X ₍₂₎ ^- in by One by anion represented, for example, iodide ion, bromide ion, chloride ion, p- toluenesulfonate ion, naphthalene disulfonic acid ion, benzenesulfonate ion, sulfate ion , Perchlorate ion, rhodane ion, and the like, which are acid anions used for ordinary cyanine dye salts.

Specific examples of the sensitizing dye used in the present invention are shown below, but the present invention is not limited to these.

[0067]

[Chemical 13]

[0068]

[Chemical 14]

[0069]

[Chemical 15]

[0070]

[Chemical 16]

[0071]

[Chemical 17]

[0072]

[Chemical 18]

[0073]

[Chemical 19]

[0074]

[Chemical 20]

[0075]

[Chemical 21]

[0076]

[Chemical formula 22]

[0077]

[Chemical formula 23]

[0078]

[Chemical formula 24]

[0079]

[Chemical 25]

[0080]

[Chemical formula 26]

[0081]

[Chemical 27]

[0082]

[Chemical 28]

[0083]

[Chemical 29] The compounds represented by the general formulas (I) and (II) used in the present invention are known compounds and can be easily synthesized by the methods described in the following documents and the like.

For example, FM Harmer (FM).
Hamer) "Heterocyclic Compounds-
Cyanine Soybean and Relative Compounds- (Heterocyclic Compound
-Cyanine dyed related
compounds-) ", John Wiley & Sons (John Wiley & Sons),
New York, London, (1964). , Day
DM Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry- (H
etheroic Compounds-Spe
cial topics in heterocycle
ic Compounds-Special topi
csin heterocyclic chemist
ry-) ”, Chapter 18, Section 14, 482-515.
Page, John Willie and Sons (John W
iley & Sons, Inc., New York, London, (1977). D.J.Fly (D.
J. Fry), "Rods Chemistry of Carbon Compounds (Rodd's Chemistr
y of Carbon Compounds) ",
(2nd. Ed. Vol. IV, part B, published in 1977), Chapter 15, pp. 369-422; (2nd.E.
d. vol. IV, part B, 1985), 15th
Chapter, pp. 267-296, Elsbayer Science Publishing Company, Inc.
r Science Publishing Comp
any Inc. ) Publications such as company publications and New York.

It is well known that addition of a certain cyanine dye is extremely effective as a means for increasing the photosensitivity of a silver halide photographic emulsion. In this case, the cyanine dye added to the silver halide photographic emulsion is adsorbed on the silver halide grains in the emulsion, and a longer wavelength absorption band is added to the absorption band specific to silver halide. This is called "spectral sensitization". On the other hand, in addition to this dye, the efficiency of color sensitization is remarkably increased by the presence of a second, specifically selected dye or other organic substance. It is known to give additive high sensitivity, and this effect is called "supersensitization". Generally, even if two or more kinds of dyes are used in combination, the sensitivity does not increase or the sensitivity decreases in many cases, so it can be said that supersensitization is an extremely unique phenomenon.

The above-mentioned supersensitization can be achieved by the combined use of the sensitizing dyes (I) and (II) preferably used in the present invention, but the present invention is not limited to these dyes. No. 1762, No. 54-34535,
56-38936, JP-A-50-28826, 51-41313, 58-153926, and 62.
A combination of the monomethine dye and the trimethine dye described in -160450 can also be used.

The addition amount of the sensitizing dye (I) is 0.02 to 3 mmol, especially 0.6 to 1.
It is preferably 2 mmol.

The addition amount of the sensitizing dye (II) is 0.02 to 3 mmol, especially 0.2 to 1.
It is preferably 2 mmol.

The addition amount of the sensitizing dye (I) is
It is preferable that the amount added is larger than that of I). The sensitizing dyes (I) and (II) may be added at any time such as during grain formation, immediately after grain formation, water washing desalting step, before chemical sensitization start and during chemical sensitization. It is preferred to be added before the addition or simultaneously with the chemical sensitizer. Also,
The addition amount of the sensitizing dyes (I) and (II) may be either first or simultaneously.

The temperature of addition of the sensitizing dyes (I) and (II) may be any temperature of 30 ° C to 90 ° C, but the range of 50 ° C to 80 ° C is preferable for the purpose of enhancing adsorption. p
H and pAg may be arbitrary, but at the time of performing chemical sensitization,
It is preferably pH 5 to 9 and pAg 7 to 10.

In the present invention, tabular silver halide grains (hereinafter referred to as tabular grains) are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane refers to the (111) plane when the ions at all lattice points on the plane side of the (111) plane have a mirror image relationship. This tabular grain has a triangular shape, a hexagonal shape, or a rounded circular shape when the grain is viewed from above, a triangular shape is a triangular shape, a hexagonal shape is a hexagonal shape, and a The shaped ones have circular parallel outer surfaces.

The tabular emulsion of the present invention has an average aspect ratio of 3
An emulsion of 100 or more and 100 or less. Here, the average aspect ratio is an average value of the aspect ratios (equivalent circle diameters of silver halide grains / grain thickness) of all tabular grains in the emulsion, and the tabular grains are grains having an aspect ratio of 2 or more. Is. The thickness of the particles can be easily calculated by, for example, depositing a metal from a diagonal direction of the particles together with a reference latex, measuring the length of the shadow on an electron micrograph, and referring to the length of the latex.

The particle diameter in the present invention is a diameter of a circle having a projected area of parallel outer surfaces of particles. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The tabular emulsion of the present invention has an average aspect ratio of 5
Above all, it is particularly preferable that the average aspect ratio is 5 to 20.

In the emulsion of the tabular emulsion of the present invention, tabular grains are preferably present in an amount of 50% (area) or more of all silver halide grains in the emulsion so that the average aspect ratio becomes 3 to 100, More preferably, it is 70% or more, and particularly preferably 85% or more.

In the present invention, the diameter of tabular grains is
It is preferably 0.15 to 5.0 μm. The thickness of the tabular grains is preferably 0.05 to 1.0 μm.

In the present invention, the size of the tabular grains may be polydisperse, but monodisperse (coefficient of variation defined below) is preferably within 25%.

Coefficient of variation = standard deviation of grain size / average grain size * 100 The tabular grains of the present invention are preferably silver iodobromide or silver iodochlorobromide containing 30 mol% or less of iodine.

The tabular grains may have at least two layered structures having a substantially different iodine composition or chlorine composition in the silver halide grain, or may have a uniform composition. For example, in an emulsion having a layered structure with different iodine composition, even an emulsion containing a high iodine layer in the core part and a low iodine layer in the outermost layer is an emulsion containing a low iodine layer in the core part and a high iodine layer in the outermost layer. May be. Furthermore, the layered structure may consist of three or more layers. The tabular grains in the present invention can be prepared by the following precipitation generating method.
That is, the dispersion medium is put into a commonly used reactor for producing a silver halide precipitate, which is equipped with a stirring mechanism. Usually, the amount of dispersion medium introduced into the reactor in the first stage is at least about 10%, preferably 20-80% of the amount of dispersion medium present in the emulsion during the final grain precipitation step. The dispersion medium initially put in the reactor is water or a peptizing agent in water, and the dispersion medium may optionally contain other components such as one or more halogens. A silver halide ripening agent and / or a metal doping agent described later is blended. The peptizer may be initially present in the reaction solution, in which case
It is preferred that the concentration is at least 10%, especially at least 20% of the total amount of peptizer present at the final stage of silver halide precipitation formation. Additional dispersion medium is added into the reactor with silver and halide salts, which can be introduced from another jet. In general, the proportion of dispersion medium is adjusted after completion of the halide salt introduction, especially in order to increase the proportion of peptizer.

Also, usually less than 10% by weight of the bromide salt used to form the silver halide grains is initially present in the reactor to control the concentration of bromide ion in the dispersion medium at the beginning of silver halide precipitation formation. To do. Here, the dispersion medium in the reactor is initially substantially free of iodine ions. This is because thick non-tabular grains are likely to be formed when iodo ions are allowed to exist before silver, bromide salt and chloride salt are added at the same time. As used herein, the phrase "substantially free of iodine ions" means that the iodine iodide is independent of the silver iodide phase (β-A) as compared with bromide ions.
As gI or γ-AgI), it means that it is present in an amount insufficient for precipitation. The iodine concentration in the reactor before introducing the silver salt is preferably maintained at less than 0.5 mol% of the total halide ion concentration in the reactor. If the pBr of the dispersion medium is too high at the beginning, the tabular grains produced will be relatively thick and the grain thickness distribution will be broad. Also, the number of non-tabular grains increases. On the other hand, pB
When r is too low, non-tabular grains are likely to be formed. Here, pBr is defined as a negative value of the logarithm of the bromide ion concentration.

During the precipitation, the silver, bromide, chloride and iodo salts are added to the reactor according to techniques well known for the precipitation of silver halide grains. Usually, an aqueous solution of a soluble silver salt such as silver nitrate is introduced into the reactor at the same time as the introduction of the bromide, chloride and iodo salts. Also, the bromide, chloride and iodo salts are introduced as an aqueous salt solution such as an aqueous solution of soluble ammonium, alkali metal (eg sodium or potassium) or alkaline earth metal (eg magnesium or calcium) halide salts. The silver salt is introduced into the reactor separately from the bromide, chloride salt and iodo salt, at least initially. The bromide salt, chloride salt and iodo salt may be added separately or introduced as a mixture.

Introduction of the silver salt into the reactor initiates the grain nucleation stage. Continued introduction of silver, bromide, chloride and iodide salts forms a population of grain nuclei that serve as precipitation sites for bromide, silver chloride and silver iodide. The grains enter the growth stage due to the precipitation of silver bromide, silver chloride and silver iodide on the existing grain nuclei. The conditions for nucleation can be based on the method described in JP-A-63-11928, but the method is not limited to this method.
For example, the nucleation temperature can be in the range of 5 to 55 ° C.

The size distribution of the tabular grains formed by the present invention is greatly influenced by the concentrations of bromide salt, chloride salt and iodo salt at the growth stage. That is, when pBr is too low, tabular grains having a high aspect ratio are formed,
The coefficient of variation of the projected area becomes extremely large. By maintaining pBr between about 2.2 and 5, tabular grains having a small coefficient of variation in projected area can be formed.

The concentration and introduction rate of silver, bromide, chloride and iodo salts may be the same as those conventionally used, provided that the above-mentioned pBr condition is satisfied. It is desirable to introduce the silver and halide salts at a concentration of 0.1-5 mol per liter. However, a wider concentration range conventionally used, for example, a range from 0.01 mol per liter to the degree of saturation can be adopted. A particularly preferred precipitation method is to increase the rate of introduction of silver and halide salts to reduce the precipitation time. The rate of introduction of silver and halide salts can be increased by increasing the rate of introduction of the dispersion medium and silver and halide salts, or by increasing the concentration of silver and halide salts in the introduced dispersion medium. . By maintaining the addition rates of silver and halide salts in the vicinity of the limit value at which formation of new grain nuclei occurs as described in JP-A-55-142329, the coefficient of variation of the projected area of grains can be further reduced. .

The amount of gelatin in the reactor at the time of the nucleation has a considerable influence on the particle size distribution. The gelatin concentration is preferably 0.5 to 10 wt%, more preferably 0.5 to 6 wt%.

In addition to this, the number of rotations of stirring and the shape of the reactor also influence the distribution of the formed particle size.

In the present invention, the stirring and mixing apparatus used for forming the tabular grains is described in US Pat. No. 3,785,
An apparatus as described in No. 777 for adding the reaction solution into the solution and mixing is preferable, and the set stirring rotation speed may be too low or too high. When the stirring rotation speed is low, the generation ratio of non-parallel twin grains increases, and when it is too high, the frequency of generation of tabular grains decreases and the size distribution also broadens.

The shape of the reactor used for forming the tabular grains is most preferably a hemispherical bottom.

The tabular silver halide grains in the present invention preferably have dislocation lines. Dislocations of tabular grains are described, for example, in J. F. Hamilton, Photo. S
ci. Eng. , 11, 57, (1967) and T.W. S
hiozawa, J .; Soc. Photo. Sci. Ja
Pan, 35, 213, (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. That is, first, the silver halide grains are taken out from the emulsion without applying a pressure capable of causing dislocation. Then, the particles are placed on a mesh for electron microscope observation, and observation by a transmission method is performed while the material is cooled so as to prevent damage (for example, printout) due to an electron beam. In this case, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly using a high-voltage electron microscope (200 kV or more for particles with a thickness of 0.25 μm). Is.

The silver halide emulsion constituting the light-sensitive material of the present invention includes, for example, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof during the process of forming tabular silver halide grains or physical ripening. A rhodium salt or its complex salt, an iron salt or an iron complex salt may coexist as a metal dopant.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Material, the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler as described in the specification, a DIR compound may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and JP-A-62-6.
3936, from the side furthest from the support, the blue-sensitive layer / GL / RL / GH / RH
It can also be arranged in the order of.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 2 mol% to about 10
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), p.648, ibid. Thirty
7105 (November 1989), pages 863-865, and "Graphide's Physics and Chemistry" by Graphide, published by Paul Montel (P. Glafkides, Chemieet).
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

The crystal structure is uniform, and the inside and the outside may have different halogen compositions, or may have a layered structure. Also, silver halides having different compositions are joined by epitaxial joining. Alternatively, it may be bonded with a compound other than silver rhodan and silver halide of lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed, or a type having a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used for the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,4.
98 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fog inside may have the same halogen composition or different halogen compositions. Examples of the silver halide whose inside or surface is fogged include silver chloride, silver chlorobromide, silver iodobromide,
Any of silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.
75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40 of the average grain size). %) Is preferable).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain size (average value of circle-equivalent diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized and spectral sensitization is not required. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 [December 1978] [November 1979] [November 1989] 1 Chemical sensitizers page 23 648 page right column 866 2 sensitivity enhancer page 648 right column 3 Spectral sensitizer, pages 23 to 24, page 648, right column to 866 to 868, supersensitizer, page 649, right column 4, whitening agent, page 24, page 647, right column, page 868, 5 antifoggant, pages 24 to 25, page 649 Right column 868-870 page Stabilizer 6 Light absorber, page 25-26 page 649 Right column-page 873 Filter dye, page 650 Left column UV absorber 7 Stain inhibitor page 25 Right column page 650 Left column-page 872 Right column 8 Dye image stabilizer Page 25 650 Page left column 872 Page 9 Hardener 26 page 651 Page left column 874 to 875 10 Binder page 26 651 Page left column 873 to 874 page 11 Plasticizer, lubricant 27 page 650 Page right column page 876 12 coating aid, page 26-27 page 650 page right column 875-876 page surfactant 13 antistatic agent page 27 page 650 right column 876-877 page 14 matting agent page 878-879 page formaldehyde gas In order to prevent the deterioration of photographic performance due to photographic properties, a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 is added to a light-sensitive material. Is preferred.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-2593
It is preferable to include the dye described in No. 58.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308,
No. 4,334,011, No. 4,327,173
West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, US Pat. Nos. 3,446,622, and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As couplers which imagewise release a nucleating agent or a development accelerator during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, and a silver halide solvent by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A R.K. D. N
o. 11449, 24241, JP-A-61-2012
47, etc., bleach accelerator releasing couplers, US Pat. No. 4,555,477, etc., ligand releasing couplers, JP-A-63-75747, leuco dye releasing couplers, US Pat. , 774,181, and the like, which release a fluorescent dye.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Esters of phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-) Diethyl dodecane amide, N, N-diethyl lauryl amide, N-tetradecyl pyrrolidone, etc.),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) , Trioctyl citrate, etc.), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
1,272-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2 described in JP-A-272248 and JP-A-1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples 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.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. As typical examples thereof, 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-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples thereof include sulfonates. Among these, especially 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in 2
It is also possible to use together more than one species.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. This black and white developer contains dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below.

That is,

[0168]

[Equation 1] The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminopolyamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644 and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-9563.
The compounds described in No. 0 are preferable. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates is preferred. It is common and in particular ammonium thiosulfate can be used most widely. It is also preferable to use a thiosulfuric acid solution in combination with thiocyanate, a thioether compound, thiourea and the like. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. The improvement of stirring is
It is considered that the bleaching agent and the fixing agent are supplied to the emulsion film faster, and as a result, the desilvering rate is increased. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such treatment is particularly effective for shortening the treatment time in each step and reducing the amount of treatment liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, the material used such as the coupler), the purpose of use, the rinsing water temperature, the number of rinsing tanks (the number of stages), the countercurrent and the countercurrent replenishment method, and other conditions. Can be set to. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows: Journalof the Society
of Motion Picture and Tel
edition Engineers Vol. 64, P.P.
248 to 253 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of water to be washed can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the resulting suspended matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society (1986).

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In some cases, the washing treatment is further followed by a stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628. .

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2 and the like.

The silver halide light-sensitive material of the present invention is effective when it is applied to the film unit with a lens described in JP-B-2-32615, JP-B-3-39784 and the like. .

[0190]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example-1 (Preparation of tabular emulsion) Aqueous solution 1 containing 10.5 g of inert low molecular weight gelatin (average molecular weight 50,000) and 3.0 g of KBr.
000 ml was kept at 30 ° C. and stirred. Silver nitrate aqueous solution (AgNO ₃ 8.2g) and halide aqueous solution (KBr
5.7 g, KI 0.35 g) was added by double jet over 1 minute. After adding 21.5 g of deionized ionic gelatin kept at 90 ° C., the temperature was raised to 75 ° C.
After the temperature was raised, 14.7N aqueous ammonia solution was added to adjust the pH to 8.
After adjusting to 3 and physically aging, 1N nitric acid was added to adjust the pH to 5.5 again. Next, a silver nitrate aqueous solution (AgNO ₃ 1
65 g) and an aqueous halogen solution (KI to KBr = 4.
The particles were grown by accelerating the flow rate with a double jet and adding it over 58 minutes. At this time, the silver potential was kept at -25 mV against the saturated calomel electrode. The resulting emulsion was desalted by the flocculation method, gelatin was added, and then the pH was adjusted to 5.5 and pAg 8.8. Average aspect ratio 11.2, sphere equivalent diameter 1.0
It was an emulsion having tabular grains of 8 .mu.m and a coefficient of variation of 24%.

Subsequently, chloroauric acid, potassium thiocyanate, and the sulfur sensitizer and / or selenium sensitizer shown in Table 1 were used to optimize the sensitivity for 1/100 sec.
Chemically sensitized at ℃.

Emulsions A to T were obtained by adding the sensitizing dyes shown in Table 1 to the respective emulsions at the addition amounts and the addition positions shown in Table 1.

[0193]

[Table 1] The emulsion prepared in this way was coated as follows for Samples 1 to 1.
Twenty created.

An emulsion and a protective layer were coated on a triacetyl cellulose film support provided with an undercoat layer in the following coating amounts. <Emulsion layer> Emulsion ... Emulsions Em-A to S shown in Table 1 (silver 1.85x)
10 ^-2 mol / m ² ) ・ Coupler (1.54 × 10 ^-3
Mol / m ² )

[0195]

[Chemical 30] ・ Tricresyl phosphate (1.10 g /
m ² ) ・ Gelatin (2.30 g /
m ² ) <Protective layer> • 2,4-dichlorotriazine-6-hydroxy-s-
Triazine sodium salt (0.08 g / m ² ) -Gelatin (1.8
0 g / m ² ) After exposing the color photographic light-sensitive material as described above, it was processed by the method described below. (Treatment method) Step Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ° C Bleach 3 minutes 00 seconds 38 ° C Water wash 30 seconds 24 ° C settling 3 minutes 00 seconds 38 ° C water wash (1) 30 seconds 24 ° C water wash (2) 30 seconds 24 ° C Stability 30 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, the composition of the treatment liquid is described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid 10.05 (bleaching solution) (unit g) ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 ethylenediaminetetraacetic acid disodium salt 10.0 3-mercapto-1,2,4-triazole 03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 (fixing solution) (unit g) ethylenediaminetetraacetic acid disodium salt 0.5 ammonium sulfite 20.0 ammonium thiosulfate aqueous solution 295.0 ml (700 g / liter) ) Acetic acid (90%) 3.3 Add water 1.0 liter pH (adjusted with ammonia water and acetic acid) 6.7 (stabilizing solution) (unit g) sodium p-toluenesulfinate 0.03 polyoxyethylene -P-Monononylphenyl 0.2 ether (average degree of polymerization 10) ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole-1) -0.75 ilmethyl) piperazine Water was added to 1.0 liter pH 8.5 The exposure was 1/100 second. Using a wedge exposure of the ordinary.

A filter is used for the light source, and
Exposure was performed through an optical filter SC-80 manufactured by Fuji Photo Film Co., Ltd., which was adjusted to a color temperature of 00 ° K.

With respect to the treated sample, the density was measured by a green filter according to a conventional method.

In the following description, the measured values relating to "fog" and "sensitivity" have the following meanings.

Fog: the minimum optical density of the characteristic curve,
The larger the value, the less preferable.

Sensitivity: Minimum optical density on the characteristic curve +0.
It is the reciprocal of the exposure amount (true value) that gives an optical density of 2,
Here, the sensitivity of Sample 1 is expressed as a relative value with 100 being set, and the larger the value, the higher the sensitivity, which is preferable.

Further, the following processing was performed in order to evaluate the gradation change with time of the latent image. After each sample was aged for 7 days in an atmosphere of a temperature of 40 ° C. and a relative humidity of 60%, the same treatment as that described above was performed to measure the concentration. This data was compared with the previous data to calculate the change in gradation over time of the latent image.

The results are shown in Table 1.

Here, the gradation is the difference in optical density between the above-mentioned sensitivity point and the exposure amount at which the exposure amount is doubled from the sensitivity point.

By using both the dyes of the present invention in combination, the fog was reduced and the change in gradation due to the latent image aging could be prevented.

Example 2 (Preparation of Normal Crystal Emulsion) <Preparation of Seed Crystal 1> 1 kg of gelatin was dissolved in 25 liters of water to adjust the pH to 5.7.
5.2 liter and 10.2 of 3.5% silver nitrate aqueous solution
% Liter of an aqueous solution of potassium bromide was added at a rate of 100 cc for 10 minutes and a rate of 600 cc for 7 minutes per minute. Further, the addition amount of the aqueous solution containing 2250 g of silver nitrate was increased by 7.5 cc per minute, and the addition was completed in 68 minutes. At this time, an aqueous solution of potassium bromide was added at the same time so as to keep the pAg at 6.7. Next, while maintaining the pAg at 7.2, it was washed with water by a coagulation sedimentation method, and 475 g of gelatin was added and redispersed to obtain a seed crystal 1 having a sphere-equivalent diameter of 0.14 μm. The termination was 20 kg. <Preparation of octahedral emulsion> 45 g of seed crystal 1 and 45 g of gelatin
g was dispersed in 1450 cc of water at 70 ° C. and the pH was adjusted to 6.5.
The pAg was controlled at 9.0 with an aqueous solution of a mixture of potassium bromide and potassium iodide containing 000 cc and 2 mol% of iodide, and the addition was performed over 60 minutes. However, the rate of addition is 1 from the beginning of addition to the end of addition.
The addition rate was increased linearly with time so that it was 2.755 times.

Next, at 35 ° C., water was washed by adjusting the pAg to 7.5 by the coagulation sedimentation method using a water-soluble polymer so that the concentration of the water-soluble salt would be 1/200.
100 g of gelatin was added, pAg = 8.4, pH = 6.
Redispersion was carried out under the condition of 4. Thus, an octahedral emulsion having a sphere equivalent diameter of 0.50 μ was obtained. <Preparation of 14-sided emulsion> It was prepared in the same manner as for the octahedral emulsion. However, the silver nitrate aqueous solution was added while controlling the pAg at the time of grain formation to 8.0. (1
Tetrahedral grains having 11) and (100) planes having substantially the same area were obtained.

Next, at 35 ° C., water was washed by adjusting the pAg to 7.5 by a coagulation sedimentation method using a water-soluble polymer so that the concentration of the water-soluble salt would be 1/200.
100 g of gelatin was added, pAg = 8.4, pH = 6.
Redispersion was carried out under the condition of 4. Thus, a tetradecahedral emulsion having a sphere equivalent diameter of 0.50 μm was obtained. <Preparation of cubic emulsion> By the same method as for the octahedral emulsion,
Created. However, the pAg at the time of particle formation is 6.6.
The aqueous solution of silver nitrate was added while controlling the above.

Next, at 35 ° C., washing with water was carried out at a concentration of the water-soluble salt of 1/200 by coagulation sedimentation method using a water-soluble polymer while adjusting pAg to 7.5.
100 g of gelatin was added, pAg = 8.4, pH = 6.
Redispersion was carried out under the condition of 4. Thus, a cubic emulsion having a sphere equivalent diameter of 0.50 μ was obtained.

Using the emulsion obtained as described above, Example 1
As a result of conducting an experiment similar to the above, it was confirmed that the embodiment of the present invention has high sensitivity and less fog, and less change in gradation with time of latent image. Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20 Second layer (intermediate) Layer) Emulsion Toggle 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion a 0.25 Emulsion ha 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1. 5 × 10 ⁻⁵ ExS-3 4.5 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0. 020 Cpd-2 0.025 HBS 1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.80 ExS-1 3.0 × 10 -4} ExS-2 1.2 × 10 -5 ExS-3 4. 0 × 10 ⁻⁴ ExC-1 0.15 ExC-2 0.060 ExC-4 0.11 ExC-7 0.0010 ExC-8 0.025 Cpd-2 0.023 HBS-1 0.10 Gelatin 0. 75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion silver 1.40 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC- 1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer (intermediate layer) ) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10 7 layers (low-sensitivity green-sensitive emulsion layer) Emulsion A silver 0.17 Emulsion B silver 0.17 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.5 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 8th layer (medium sensitivity green feeling) Emulsion layer) Emulsion silver 0.80 ExS- ⁴ 2.0x10 ^-5 ExS-5 1.4x10 ^-4 ExS-6 5.4x10 ^-4 ExM-2 0.16 ExM-3 0. 045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90 9th layer (high-sensitivity green emulsion layer) Emulsion silver 1.25 ^{ExS-4 3.7 × 10 -5 ExS} -5 8.1 × 10 -5 ExS-6 3.2 × 10 -4 ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20 10th layer (yellow filter layer) Yellow colloidal silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low sensitivity blue emulsion layer) Emulsion ha 0.25 Emulsion silver 0.40 ExS-78 0.0 × 10 ⁻⁴ ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.35 Gelatin 1.30 12th layer ( High-sensitivity blue-sensitive emulsion layer) Emulsion silver 1.38 ExS-7 3.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 gelatin 0.86 13th layer 1 protective layer) Agent preparative silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 -2 Gelatin 1.00 14th layer (second protective layer) H-1 0.40 B-1 (Diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (Diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Further, storability is appropriately set for each layer, Processability, pressure resistance, mildew-proof
W-1 for improving antibacterial property, antistatic property and coating property
To W-3, B-4 to B-6, F-1 to F-
17 and iron salts, lead salts, gold salts, platinum salts, iridium salts,
Palladium salt and rhodium salt are contained.

[0210]

[Table 2] In Table 2, (1) Emulsions (a) to (e) were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions a to f were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope.

[0211]

[Chemical 31]

[0212]

[Chemical 32]

[0213]

[Chemical 33]

[0214]

[Chemical 34]

[0215]

[Chemical 35]

[0216]

[Chemical 36]

[0217]

[Chemical 37]

[0218]

[Chemical 38]

[0219]

[Chemical Formula 39]

[0220]

[Chemical 40]

[0221]

[Chemical 41]

[0222]

[Chemical 42]

[0223]

[Chemical 43]

[0224]

[Chemical 44] Sample 102 was prepared by changing the sensitizing dyes of the fifth and ninth layers to the sample 101 as follows. Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion silver 1.40 ExS-1 1.8 × 10 ⁻⁴ ExS-2 0.9 × 10 ⁻⁵ ExS-3 2.7 × 10 ⁻⁴ ExS-7 5.1 × 10 ^-5 ExC-1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 9th layer (high sensitivity green emulsion layer) Emulsion silver 1.25 ExS-4 3.33 × 10 ⁻⁵ ExS-5 7.29 × 10 ⁻⁵ ExS-6 2.88 × 10 ⁻⁴ ExS-7 4.38 × 10 ^-5 ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-20 .10 Gelatin 1.20 The same experiment as in Example 1 was performed for Samples 101 and 102. Was Tsu, sample 102 to the sample 101, the effect of the present invention that the gradation changes in the latent image over time is small was confirmed.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
Halogen characterized in that the silver halide grains in the emulsion layer are selenium-sensitized, and the emulsion layer contains at least one trimethine cyanine dye and at least one monomethine cyanine dye. Silver halide photographic light-sensitive material. 2. At least one of the trimethine cyanine dyes.
2. The silver halide photographic light-sensitive material according to claim 1, further comprising selenium-sensitized silver halide grains in the presence of at least one monomethinecyanine dye. 3. The silver halide photographic light-sensitive material according to claim 1, which contains an emulsion containing silver halide grains having an average aspect ratio of 3 or more and 100 or less.