JPH08201952A - Chemical sensitization method for silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the silver halide photographic sensitive material high in sensitivity and superior in latent image stability and improved in high- illumination reciprocity law failure characteristics by using at least one kind of specified compound. CONSTITUTION: At least one kind of compound to be used is represented by the formula in which R1 is an alkyl, alkenyl, cycloalkyl, or aryl group; and Y is a nonmetallic atomic group necessary to form a 5-, 6-, 7-, or a 8-membered heterocyclic group together with the N atom. An emulsion contains silver halide grains each having an aspect ratio of >=2 in an amount of >=50% of the projection areas of the total silver halide grains are chemically sensitized by at least one of an Se or Te compound in the presence of a sensitizing dye or an N-containing hetero-cyclic group after reduction sensitization. The silver halide grains amounting to >=50 number % of the total silver halide grains have >=10 dislocation lines per each grain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for chemically sensitizing a silver halide photographic emulsion, and more specifically to high sensitivity and low fog,
And a method for chemically sensitizing a silver halide photographic emulsion capable of improving latent image stability and illuminance failure characteristics. Further, the present invention relates to a silver halide photographic light-sensitive material (hereinafter also simply referred to as "light-sensitive material") having the chemically sensitized silver halide emulsion.

[0002]

2. Description of the Related Art In recent years, the sensitivity of popular type photosensitive materials has been remarkably increased, and photography has become easier and more convenient. In particular, recently, with the widespread use of photography equipment called compact cameras and lens-equipped films, photography in various scenes has been carried out, and the demand for higher sensitivity of photosensitive materials has never tired of being involved in development. It is an eternal theme for people.

Further, due to the daily use of photography, the time (month / day) from photography to development often passes for a long time (period). If a long time elapses between shooting and development, the latent image generated by exposure will regress over time, so-called "latent image regression" becomes a major problem, and therefore latent image stability is also excellent. This is one of the essential conditions for photosensitive materials. Further, with the increase in the use of cameras with strobes, it is required to further improve illuminance failure characteristics.

[0004] As a study for increasing the sensitivity, various techniques for forming a light-sensitive material have been studied. As far as silver halide grains are concerned, adjustment of grain shape and halogen composition,
Introducing dislocation lines, etc., for chemical sensitization and spectral sensitization, research on new sensitizers (for example, selenium, tellurium, etc.), control of silver sulfide nucleation by combination with other additives, Control of dye adsorption has been studied, but all of them have advantages and disadvantages. That is, even if high sensitivity is achieved, it is difficult to satisfy the latent image stability and illuminance failure characteristics.

[0005]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity, excellent latent image stability, and improved illuminance failure characteristics.

[0006]

The above objects of the present invention have been achieved by the following constitutions. That is, (1) A method for chemically sensitizing a silver halide photographic emulsion using at least one compound represented by the general formula (I) [Chemical Formula 1].

(2) A method for chemically sensitizing a silver halide photographic emulsion using at least one compound represented by the general formula (II) [Chemical formula 2].

(3) The silver halide photograph as described in (1) or (2), which chemically sensitizes an emulsion in which silver halide grains having an aspect ratio of 2 or more are present at 50% or more of the projected area of all silver halide grains. Chemical sensitization method of emulsion.

(4) The photographic silver halide emulsion as described in (1), (2) or (3), which is chemically sensitized in the presence of a sensitizing dye or a nitrogen-containing heterocyclic compound.

(5) The chemical sensitization of the photographic silver halide emulsion according to any one of (1) to (4), wherein the silver halide emulsion to be chemically sensitized is previously subjected to reduction sensitization. Method.

(6) The chemical sensitization method for photographic silver halide emulsions according to any one of (1) to (5), wherein the chemical sensitization is at least one of selenium sensitization and tellurium sensitization.

(7) The silver halide emulsion has a total grain number of 50
The chemical sensitization method for photographic silver halide emulsions according to any one of (1) to (6), wherein at least 10% has 10 or more dislocation lines per grain.

(8) A silver halide emulsion in which 50% or more of all grains have 10 or more dislocation lines per grain is used, and at least one compound represented by the general formula (III) [Chemical Formula 3] is used. Chemical sensitization method of silver halide photographic emulsion.

(9) A silver halide photographic light-sensitive material containing a silver halide photographic emulsion chemically sensitized by the chemical sensitization method described in any one of (1) to (8).

The present invention will be described in detail below.

First, the compound represented by formula (I) will be specifically described.

[0017]

[Chemical 4]

In the formula, R ₁ is an alkyl group, an alkenyl group,
It represents a cycloalkyl group or an aryl group, and Y represents a non-metal atom group necessary for forming a 5- to 8-membered heterocycle with a nitrogen atom.

Examples of the alkyl group represented by R ₁ include methyl, ethyl, butyl, octyl, dodecyl, tetradecyl and hexadecyl groups, and examples of the alkenyl group include ethenyl and propenyl groups. .

Examples of the cycloalkyl group include a 5- to 7-membered cycloalkyl group which may have a substituent (cyclopentyl, cyclohexyl, etc.).

As the aryl group, for example, a phenyl group,
A naphthyl group can be mentioned.

Each of the above groups may have a substituent, and examples of the substituent include alkyl, aryl, alkoxy,
Carbonyl, carbamoyl, acylamino, sulfamoyl, sulfonamide, carbonyloxy, alkylsulfonyl, arylsulfonyl, hydroxyl, heterocycle, alkylthio, arylthio and the like groups,
These substituents may further have a substituent.

The 5- to 8-membered heterocycle formed by Y and a nitrogen atom preferably has at least two heteroatoms. In this case, it is not preferred that at least two heteroatoms are adjacent to each other. Examples of the 5- to 8-membered heterocycle include pyrrolidine, piperidine, piperazine,
Examples thereof include morpholine, pyridine, thiamorpholine, imidazolidine, homopiperazine, 4-sulfopiperidine and the like.

The heterocycle may have a substituent, and examples of the substituent include an alkyl group and an aryl group. An aromatic ring such as a benzene ring may be condensed with the heterocycle. Furthermore, the present invention also includes the case where the carbon atom in the heterocycle becomes a spiro carbon atom.

Among the compounds represented by the general formula (I), the compound represented by the following general formula (Ia) is preferable.

[0026]

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In the formula, R ₂ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group,
It represents a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group, R ₃ represents a group capable of substituting on the benzene ring, and m represents an integer of 0 to 4. When m is 2 or more, a plurality of R _{3 s} may be the same or different, and R _{3 s} may form a ring.

Y'represents a nonmetallic atom group having the same meaning as Y in formula (I).

In the formula (Ia), the alkyl group represented by R ₂ is a linear or branched alkyl group having 1 to 24 carbon atoms (methyl, ethyl, i-propyl, t-butyl, 2- Ethylhexyl, dodecyl, t-octyl, benzyl etc.) are preferred.

The cycloalkyl group is preferably a cycloalkyl group having 5 to 24 carbon atoms (cyclopentyl, cyclohexyl, etc.).

The alkenyl group is preferably an alkenyl group having 3 to 24 carbon atoms (allyl, 2,4-pentadienyl, etc.).

Examples of the aryl group include phenyl and naphthyl groups.

Examples of the heterocyclic group include pyridyl, imidazolyl and thiazolyl groups.

Examples of the acyl group include acetyl and benzoyl groups.

Examples of the bridged hydrocarbon group include bicyclo
[2.2.1] Heptyl group and the like can be mentioned.

Examples of the alkylsulfonyl group include dodecylsulfonyl group and hexadecylsulfonyl group, and examples of the arylsulfonyl group include phenylsulfonyl group.

Each of these groups also includes those having a substituent, and examples of the substituent of the alkyl group include a halogen atom and hydroxyl, alkoxy, aryl, acylamino, sulfonamide, aryloxy, alkylthio, carbamoyl, sulfamoyl, alkyl. Examples thereof include sulfonyl, nitro, cyano, arylsulfonyl, carboxyl, amino, aryliamino, alkylamino, alkoxycarbonyl, acyl and acyloxy groups, and the substituent of the group represented by R ₂ other than an alkyl group is the above. A substituent and an alkyl group are mentioned.

Preferred as R ₂ is an alkyl group.

The group capable of substituting on the benzene ring represented by R ₃ is not particularly limited, but typical examples thereof include a halogen atom and alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, acyl, acylamino, sulfonamide. (Alkyl sulfonamide,
Arylsulfonamide, etc.), alkoxycarbonyl,
Carbamoyl (alkylcarbamoyl, arylcarbamoyl, etc.), ureido (alkylureido, arylureido, etc.), sulfamoyl (alkylsulfamoyl, arylsulfamoyl, etc.), amino (including substituted amino), sulfonyl, nitro, cyano, carboxyl, etc. Among these groups, preferred as R ₃ are halogen atom, alkyl group, alkylthio group, acylamino group and sulfonamide group.

The group represented by R ₃ may further have a substituent.

M represents an integer of 0 to 4, preferably 0.
~ 2.

R _{3 s} may form a ring. R ₃ may combine with —OR ₂ to form a ring.

-OR ₂ is

[0044]

[Chemical 6]

It can be in any position relative to, but is preferably in the para position.

The representative examples of the compounds represented by formula (I) are shown below, but the invention is not limited thereto.

[0047]

[Chemical 7]

[0048]

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[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

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[0055]

[Chemical 15]

[0056]

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[0057]

[Chemical 17]

[0058]

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[0059]

[Chemical 19]

Next, the compound represented by the general formula (II) will be specifically described.

[0061]

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In the formula, R ₁₆ is an alkyl group, an alkenyl group,
Cycloalkyl group, aryl group, heterocyclic group or -Si
Represents (R ₁₇ ) (R ₁₈ ) (R ₁₉ ). Here, R ₁₇ , R ₁₈ and R ₁₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group or an aryloxy group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R
₁₅ may be the same or different, each is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group,
It represents an acylamino group, a sulfonamide group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom or a —OR ₂₀ group. Here, R ₂₀ represents a group having the same meaning as R ₁₆ . R ₁₆ and R ₁₁ , R ₁₁ and R _12, or R ₁₂ and R ₁₃ may be bonded to each other to form a 5-membered ring, a 6-membered ring or a spiro ring.

The alkyl group represented by R ₁₆ is a linear or branched alkyl group having 1 to 24 carbon atoms, such as methyl,
Examples thereof include ethyl, i-propyl, t-butyl, octyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, eicosyl and benzyl groups.

The cycloalkyl group has 5 to 24 carbon atoms.
And cycloalkyl groups such as cyclopentyl and cyclohexyl.

The alkenyl group has 2 to 24 carbon atoms, for example, ethenyl, propenyl, butenyl,
Each group such as octenyl, decenyl, oleyl and the like can be mentioned.

Examples of the aryl group include a phenyl group and a naphthyl group.

The heterocyclic group is preferably a 5- to 8-membered ring,
Examples include pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, pyridyl, thiamorpholinyl, imidazolidinyl, thiazolidinyl, homopiperazinyl, 4-sulfopiperidyl and the like.

When R ₁₆ represents --Si (R ₁₇ ) (R ₁₈ ) (R ₁₉ ),
Examples of the alkyl group, alkenyl group, and aryl group represented by R ₁₇ , R ₁₈ , and R ₁₉ include the same groups as those described for R ₁₆ , which constitute an alkoxy group, an alkenoxy group or an aryloxy group. The alkyl, alkenyl, or aryl component is also the same as described for R ₁₆ .

Examples of the alkyl group, cycloalkyl group, alkenyl group and aryl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same as those described for R _16. You can

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the acylamino group include groups such as acetylamino and benzoylamino.

Examples of the sulfonamide group include groups such as methylsulfonylamino and benzenesulfonylamino.

The alkyl component forming the alkylamino group and the alkylthio group may be the same as the above alkyl group, and the aryl component forming the arylthio group may be the same as the above aryl group.

Examples of the alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl and benzyloxycarbonyl, and examples of the aryloxycarbonyl group include phenoxycarbonyl group.

In the general formula (II), among the respective substituents, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, or a group partially containing these may further have a substituent. .

For example, as the substituent of the alkyl group or the cycloalkyl group, a halogen atom and hydroxyl, alkoxy, alkylthio, acylamino, sulfonamide, aryl, aryloxy, carboxyl, amino, alkylamino, arylamino, carbamoyl,
Examples thereof include sulfamoyl, alkylsulfonyl, arylsulfonyl, nitro, cyano, alkoxycarbonyl, acyl and acyloxy groups.

Examples of the substituent of the group other than the alkyl group include the above-mentioned substituents and alkyl groups.

As the substituent which the aryl group and the heterocyclic group may have, a halogen atom and alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl and ureido. , Alkoxycarbonyl, amino, sulfonyl, nitro, cyano, carboxyl and the like.

The 5- or 6-membered ring which may be formed by the bond of R ₁₆ and R ₁₁ includes a chroman ring and the like, and the spiro ring includes a spirovicumaran ring and the like.

As the 5- or 6-membered ring which may be formed by combining R ₁₁ and R ₁₂ or R ₁₂ and R ₁₃ with each other, an indane ring, a coumaran ring, a naphthalene ring, a chroman ring and the like are spiro rings. Examples thereof include a spirobiindane ring, a spirobicoumaran ring, a spirobichroman ring, and the like.

These compounds are described in US Pat. No. 3,432,300
No., No. 3,573,050, No. 3,574,627, No. 3,700,455,
3,764,337, 3,935,016, 3,982,944, 4,2
54,216, JP-B-48-31625, 54-12337, JP-A-51
-152225, 53-17729, 53-17729, 53-20327
No. 54-145530, No. 55-6321, No. 55-21004, British Patent No. 1,347,556, British Patent Publication No. 2,062,888, No. 2,066,
975, 2,077,455 and the like.

Typical examples of the compound represented by formula (II) are shown below, but the invention is not limited thereto.

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

[0088]

[Chemical formula 26]

[0089]

[Chemical 27]

[0090]

[Chemical 28]

[0091]

[Chemical 29]

[0092]

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[0093]

[Chemical 31]

[0094]

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Next, the compound represented by formula (III) will be specifically described.

[0096]

[Chemical 33]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group,
It represents an aryl group, an acylamino group, a sulfonamide group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom or an alkoxy group. However, R _{21 to} R
Not all ₂₅ are hydrogen atoms. Also, R _{21 to} R ₂₅
Any two adjacent to each other may combine with each other to form a 5-membered ring, a 6-membered ring or a spiro ring.

The alkyl group, cycloalkyl group, alkenyl group and aryl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are the same as those described for R ₁₆ in the general formula (II). Similar groups may be mentioned.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the acylamino group include groups such as acetylamino and benzoylamino.

Examples of the sulfonamide group include groups such as methylsulfonylamino and benzenesulfonylamino.

Examples of the alkyl component forming the alkylamino group and alkylthio group are the same as the above-mentioned alkyl group, and examples of the aryl component forming the arylthio group are the same as the above-mentioned aryl group.

Examples of the alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl and benzyloxycarbonyl, and examples of the aryloxycarbonyl group include phenoxycarbonyl group.

In the general formula (III), among each substituent,
The alkyl group, the cycloalkyl group, the aryl group or the heterocyclic group, or the group partially having these may further have a substituent, and the substituent is as described in the above general formula (II). The same groups as those mentioned above can be mentioned.

Examples of the substituent of the group other than the alkyl group include the above-mentioned substituents and alkyl groups.

Further, as the substituent which the aryl group and the heterocyclic group may have, each group detailed in the above general formula (II) can be mentioned.

Further, as the 5-membered ring and the 6-membered ring which may be formed by bonding adjacent two of R _{21 to} R ₂₅ , an indane ring, a coumarane ring, a naphthalene ring, a chroman ring, etc. Examples of the spiro ring include a spirobiindane ring, a spirobicoumaran ring, and a spirobichroman ring.

These compounds include the compounds described in the references cited in the above general formula (II).

Typical examples of the compound represented by the general formula (III) are shown below, but the invention is not limited thereto.

[0110]

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[0111]

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[0112]

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The chemical sensitization in the present invention means from the start of at least one of the spectral sensitization step and the chemical sensitization step to the end of the later step.

In the present invention, at least one selected from the spectral sensitization step and the chemical sensitization step is started.
After particle formation (when required, desalting is completed)
After adjusting pH, pAg, temperature, etc. to an arbitrary value, it means the time when the additive for sensitization is added for the first time, and the end of the sensitization is stable for the optimum time, after spectral or chemical sensitization. It means the point of time at which an agent (a compound having a function of stopping Ostwald ripening or chemical ripening and suppressing an unnecessary increase in fog).

Here, the additives relating to sensitization include various sensitizers such as sulfur sensitizers, selenium sensitizers, tellurium sensitizers, spectral sensitizing dyes, supersensitizers and silver halide solvents. It is an additive added to the emulsion during sensitization.

The halide composition of the silver halide emulsion is preferably silver iodobromide or silver bromide.

The silver halide grains contained in the silver halide emulsion are preferably those having a regular crystal form such as a cube, octahedron or tetradecahedron, or tabular grains, particularly (111) dihedral grains. Twinned silver halide grains having crystal faces are preferred. A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the report Photographishe Korrespondenz. ) Volume 99,
For details, see page 99, volume 100, page 57.

When tabular silver halide grains are used, it is preferred that grains having a ratio of grain size to thickness of tabular grains (called an aspect ratio) of 2 or more are present in an amount of 50% or more of the projected area of all grains. It is more preferable that 70% or more of particles of 3 or more and less than 20 are present.

The average grain size r of the silver halide grains is 0.
It is preferably 1 μm or more (particularly 0.2 μm or more, further 0.3 μm or more), and 5.0 μm or less (particularly 4.0 μm or less, further 3.0 μm or less). The average particle diameter r is defined as the average volume diameter based on the product (ni × ri ³ ) of the frequencies ni and ri ^{3 of} particles having the particle diameter ri.

The grain size referred to here is the diameter when a projected image of a silver halide grain is converted into a circular image having the same area. The particle size can be obtained, for example, by magnifying the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is not measured). Discrimination shall be 1,000 or more).

The silver halide emulsion is preferably a monodisperse emulsion. Here, the monodisperse emulsion is defined as the breadth of the grain size distribution (%) = (standard deviation / average grain size) × 100. 20% or less. Further, in the present invention, it is preferable that the width of the distribution is 15% or less. Here, the average particle size and the standard deviation are obtained from the particle size ri defined above and the frequency ni of the particles having the particle size ri.

The average silver iodide content in the entire silver halide grains is 1 mol% or more (particularly 2 mol% or more, further 3 mol%).
Or more) is preferable, and 15 mol% or less (particularly 12 mol% or less,
Furthermore, 10 mol% or less) is preferable.

The silver halide composition structure of the silver halide grains is preferably such that the silver halide composition is continuously changed or a core / shell structure is adopted in order to efficiently achieve sensitization.

In this case, it is preferable to have a high silver iodide-containing phase having a silver iodide content of 8 mol% or more (particularly 10 mol% or more, further 20 mol% or more) inside the grain. However, the content is good enough not to precipitate the silver iodide phase, and is preferably 45 mol% or less (particularly 40 mol% or less). Further, the outermost phase of the silver halide grain having a high silver iodide content phase inside the grain is preferably formed of a low silver iodide content phase having a lower silver iodide content than the high silver iodide content phase. The silver iodide content of the low silver iodide-containing phase forming the outermost phase is preferably 10 mol% or less (particularly 6 mol% or less, more preferably 4 mol% or less).

An intermediate phase having a different silver iodide content may be present between the outermost phase and the high silver iodide containing phase. The silver iodide content of the intermediate phase is preferably 10 mol% or more (particularly 12 mol% or more), and 22 mol% or less (particularly 20 mol% or less). The silver iodide contents of the outermost phase and the intermediate phase, and the silver iodide contents of the intermediate phase and the high silver iodide containing phase are preferably 6 mol% or more, particularly preferably 10 mol% or more. Good.

In the above embodiment, the central part of the internal high silver iodide containing phase, the internal high silver iodide containing phase and the intermediate phase, or
Another silver halide phase may be present between the intermediate phase and the outermost phase.

The volume of the outermost phase is preferably 4% or more (particularly 10% or more) of the total particles, and 70% or less (particularly 50%).
The following) are preferable. The volume of the high silver iodide-containing phase is
10% or more (especially 20% or more) is preferable, and 80% or less (especially 50% or less) is preferable. The volume of the intermediate phase is preferably 5% or more (particularly 20% or more) of the whole particles, and 60% or less (particularly 55% or less).

These phases are composed of a single phase having a substantially uniform composition, a phase group consisting of a plurality of phases having a uniform composition, the composition of which changes stepwise, or a continuous composition in which the composition continuously changes in an arbitrary phase. Either the phase or a combination thereof may be used.

The silver halide grains contained in the silver halide emulsion of the present invention are prepared by preliminarily allowing an aqueous solution containing a protective colloid and seed grains to be present in a reaction vessel and, if necessary, adding silver ions, halogen ions or silver halide fine grains. It is obtained by supplying and crystallizing seed particles. Here, the seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed grains is arbitrary, silver bromide,
It may be any of silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide and silver chloroiodobromide, but silver bromide and silver iodobromide are preferred.

When seed particles are used in the present invention, the seed particles may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or an irregular shape such as a sphere or a plate. It may have a crystalline form. In these particles,
Any ratio of (100) plane to (111) plane can be used. Further, although those having a composite form of these crystal forms may be used and grains of various crystal forms may be mixed, it is preferable to use spherical seed grains having two opposing parallel twin planes.

As the means for forming the silver halide emulsion of the present invention, various methods well known in the art can be used. That is, the single jet method, the double jet method
The jet method, the triple jet method and the like can be used in any combination. Further, a method of controlling pH and pAg in the liquid phase in which silver halide grains are produced according to the growth rate and stage of silver halide grains can also be used. The silver halide emulsion can be produced by any of the acidic method, the neutral method and the ammonia method.

In the production of the silver halide emulsion, the halide ion and the silver ion may be mixed at the same time, or the other may be mixed in the presence of either one. Further, while considering the critical growth rate of silver halide crystals, halide ions and silver ions may be sequentially or simultaneously added to the mixing vessel while controlling pAg and pH to grow. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel. In the production of silver halide emulsion, a known silver halide solvent such as ammonia, thioether or thiourea can be present.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be contained. When removing the salts, Research Disclosure (Resear
ch Disclosure, hereinafter abbreviated as RD) No. 17643, Item II.

The silver halide grains according to the present invention are preferably subjected to reduction sensitization in advance, and particularly those having reduction sensitization inside the grains are preferable. The inside of the particle referred to here is a portion closer to the center than the inner 90% of the volume of the whole particle, and preferably a portion closer to the center than the inner 70%.

Reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth, or by adding this solution.
The ripening or grain growth of the emulsion is carried out under a low pAg condition of pAg = 7 or less or a high pH condition of pH = 7 or more.

A silver salt can be added to obtain a low pAg condition, and a water-soluble silver salt is preferable. Silver nitrate is preferred as the water-soluble silver salt. The pAg during aging is suitably 7 or less, preferably 6 or less, more preferably 1 to 3.
Note that pAg = -log [Ag ⁺ ]. Reduction sensitization under a high pH condition is carried out by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or the like can be used. When ammoniacal silver nitrate is used for silver halide formation, an alkaline compound excluding ammonia is preferably used.

As a method for adding the silver salt or the alkaline compound for reduction sensitization, rush addition may be carried out or addition may be carried out over a certain period of time. When it takes a certain time,
It may be added at a constant flow rate, or may be added by changing the flow rate like a function. Also, the required amount may be added in several divided portions. Prior to the addition of the soluble silver salt and / or the soluble halide into the reaction vessel, it may be allowed to exist in the reaction vessel or mixed in the solution of the soluble halide,
You may add with a halide. Furthermore, the addition may be performed separately from the soluble silver salt and the soluble halide.

In the preparation of silver halide emulsion, a method of growing from seed grains is preferably used. Specifically, it is obtained by preliminarily allowing an aqueous solution containing a protective colloid and seed particles to exist in a reaction vessel, and optionally supplying silver ions, halogen ions or silver halide particles to grow the seed particles. . Seed particles can be prepared by a single jet method, a controlled double jet method or the like well known in the art. The halogen composition of the seed grains is arbitrary, and silver bromide, silver iodide, silver chloride,
It may be any of silver iodobromide, silver chloroiodide, silver chlorobromide, and silver chloroiodobromide, but silver bromide and silver iodobromide are preferable, and in the case of silver iodobromide, average iodide is used. The silver content is preferably 1 to 20 mol%.

In the case of growing from seed grains, in low pAg ripening, it is preferable to add silver nitrate for ripening after the formation of the seed emulsion, that is, immediately before desalting of the seed grains to after desalting. In particular, it is preferable to add silver nitrate after the desalting of the seed particles for ripening, and the ripening temperature is preferably 40 ° C. or higher and 50 ° C. to 80 ° C. Aging time is 30 minutes or more, preferably 50 to 150 minutes.

In the case of growing from seed grains, in the high pH ripening, the grains can be grown at least once in an environment of pH 7 or more until a portion corresponding to 70% of the volume of the grown grains grows. More preferably, it is more preferable to grow the particles through an environment of pH 7 or more until the portion corresponding to 50% of the volume of the grown particles grows, and to correspond to 40% of the volume of the grown particles. Most preferably, the grains are grown at least once in an environment of pH 8 or more before the growing portion grows.

An internally reduction-sensitized halo used in the present invention
An oxidizing agent should be used for emulsions composed of silver genide grains.
Preferably, specifically, H₂O₂， NaBO₂， H₂O₂・ 3H₂O₂, Na_Four
P₂O₇・ 2H₂O₂， 2Na₂SO_Four・ H₂O₂・ 2H₂Hydrogen peroxide (water) such as O
And its additions, K₂S₂O₃， K₂C ₂O₃， K_FourP₂O₃， K₂[Ti (O₂) C
₂O_Four] 3H₂Peroxy acids such as O, peracetic acid, ozone, iodine,
Examples thereof include bromine and thiosulfonic acid compounds. The addition
You can add it anywhere in the silver halide emulsion manufacturing process.
Yes. It can also be added prior to the addition of the reducing agent.
Also, after adding the oxidizing agent, it is necessary to neutralize the excess oxidizing agent.
For this purpose, a reducing substance can be newly added.

These reducing substances are substances capable of reducing the above-mentioned oxidizing agents, and include sulfinic acids, di- and trihydroxybenzenes, chromanes, hydrazines and hydrazides, p-phenylenediamines, aldehydes,
Examples include aminophenols, enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives.

In the present invention, especially 50% of the total number of particles is used.
The effect of the present invention is obtained by the chemical sensitization method of chemically sensitizing a silver halide photographic emulsion having 10 or more dislocation lines per grain with at least one compound represented by the general formula (III). Play.

The dislocation lines of the silver halide emulsion according to the present invention are incorporated into the silver halide grain by intentionally introducing a controlled recrystallization process of the silver halide grain in the preparation of the silver halide emulsion grain. You can There are various methods for observing dislocation lines, as described, for example, in the Japan Institute of Metals: New Edition "Dislocation Theory-Application to Metallurgy", Maruzen, l971, pp.627-645. Direct observation with an electron microscope is possible. Regarding the number of dislocation lines, "The Theory of the Photographic Process", 3rd edition, edited by James, TH, New York, McClamine, 1967, p. 17, "Dislocations found in emulsion crystals" The number of lines is usually small, 5-10, but it is 0 for some silver halide precipitations. "

The number of dislocation lines may be 10 or more on average per grain of 50% or more of the total number of silver halide grains in the emulsion, but 20 or more on average per grain. It is preferable to have dislocation lines, and it is particularly preferable to have an average of 30 or more dislocation lines per grain.

In the present invention, the number of dislocation lines is 30 or more, preferably 30 to 10,000. In the area of more than 10,000 lines, it is difficult to check the number and the photographic characteristics are not improved.

To introduce dislocation lines into a silver halide crystal, it is necessary to disorder the periodic structure of the crystal aperiodically. That is, a foreign ion or an organic compound different from the halogen ion and silver ion used for the growth of silver halide is introduced in the middle of the crystal growth process so that the lattice constant changes discontinuously at a certain position of the crystal lattice. Alternatively, dislocation lines can be introduced by supplying halogen ions and silver ions so that the halogen composition changes abruptly.
When an organic compound is added for this purpose, it is preferable that it interacts with the silver halide in some way. Specifically, sensitizing dyes and stabilizers commonly used in the art can be used for this purpose. Examples of the method of rapidly changing the composition of silver halide include a method of adding a potassium iodide solution during the formation of silver bromide grains and a method of growing silver iodide or silver chloride during the formation of silver bromide grains. And then ripening or subsequently adding further silver bromide grain formation. On the contrary, there is also a method in which Ag ⁺ and Br ⁻ are added to a system of small-sized core particles having an extremely high iodine composition to cause remarkable recrystallization. In short, crystallization may be performed so that when the silver halide minimizes the formation energy of the crystal lattice during the growth process, the lattice constant stabilizes in a state where the lattice constant suddenly changes in a certain region of the crystal lattice.

In the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used as the chemical sensitizer.

As the sulfur sensitizer applicable in the present invention, 1,3-diphenylthiourea, triethylthiourea,
Preferred examples include thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, sodium thiosulfate, and simple sulfur. Note that α-sulfur belonging to the orthorhombic system is preferable as the simple substance of sulfur. Other sulfur sensitizers include U.S. Patents 1,574,944 and 2,410,689.
No., No. 2,278,947, No. 2,728,668, No. 3,501,313,
Specifications such as 3,656,955, West German application publication (OLS)
The sulfur sensitizers described in 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used.

The selenium sensitizers that can be used in the present invention include a wide variety of selenium compounds. For example, US Pat.
No. 4, No. 1,602,592, No. 1,623,499, JP-A-60-150046
JP-A-4-25832, JP-A-4-109240 and JP-A-4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg allyl isoselenocyanate), selenoureas (eg N, N-).
Dimethylselenourea, N, N, N'-triethylselenourea,
N, N, N′-trimethyl-N′-heptafluoroselenourea,
N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg selenoacetone, selenoacetophenone) etc),
Selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropionic acid, methyl
-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate), and selenides (dimethyl selenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. US Patent 1,574,
944, 1,602,592, 1,623,499, 3,297,466
Issue 3,297,447, 3,320,069, 3,408,196,
3,408,197, 3,442,653, 3,420,670, 3,5
91,385, French Patents 2,693,038, 2,093,209,
Japanese Patent Publications No. 52-34491, No. 52-34492, No. 53-295, and No. 57-2
2090, JP-A-59-180536, 59-185330, 59-181
337, 59-187338, 59-192241, 60-150046
No. 60-151637, No. 61-246738, JP 3-4221,
3-24537, 3-111838, 3-116132, 3-14864
No. 8, No. 3-237450, No. 4-16838, No. 4-25832, No. 4-3
2831, 4-96059, 4-109240, 4-140738,
4-140739, 4-147250, 4-149437, 4-1843
No. 31, No. 4-190225, No. 4-119729, No. 4-1995035, British Patent Nos. 255,846, 861,984, HESpencer et al., J.Phot.Sci. 31, 158-169 ( 1983) and other research papers.

Tellurium sensitizers and sensitizing methods which can be used in the present invention are described in US Pat. Nos. 1,623,499 and 3,320,069,
3,772,031, 3,531,289, 3,655,394, British Patents 235,211, 1,121,469, 1,295,462, 1,3
96,696, Canadian Patent 800,958, Japanese Patent Laid-Open No. 4-20464, and the like. Examples of useful tellurium sensitizers include telluroureas, telluroamides and the like.

The addition amount of the sulfur sensitizer, the selenium sensitizer, and the tellurium sensitizer is not uniform depending on the kind of silver halide emulsion, the kind of compound used, the ripening conditions, etc. It is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

In the chemical sensitization of the present invention, the sensitivity can be further increased by using gold sensitization together. Examples of useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, U.S. Patents 2,597,856, 5,049,484, and 5,049,
No. 485, Japanese Examined Patent Publication No. 44-15748, JP-A 1-147537, No. 4-706
Examples thereof include gold complexes of organic compounds disclosed in No. 50 and the like.

The above-mentioned various sensitizers may be added by adding them by dissolving in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, or by adding gelatin depending on the properties of the compound to be used. A method of mixing with a solution in advance and adding it may be a method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

In the present invention, when the chemical sensitization is carried out in the presence of a sensitizing dye or a nitrogen-containing heterocyclic compound, the effect of the present invention is further exhibited. The heterocyclic compound is described in JP-A-58-1
The sensitizing dyes and nitrogen-containing heterocyclic compounds disclosed in Nos. 26526 and 59-193448 can be used.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with a sensitizing dye, it is a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light.
A supersensitizer that enhances the sensitizing action of the sensitizing dye may be contained in the emulsion.

Examples of the sensitizing dye include polymethine dyes containing cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl and hemioxonol dyes, oxonol, merostyryl and streptocyanine.

Antifoggants and stabilizers include tetrazaindenes, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc., and mercaptopyrimidines, mercaptotriazines, such as thioketo such as oxazolithion. Compounds, further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives,
Examples thereof include ascorbic acid derivatives.

In the present invention, good results are often obtained when sensitization is carried out in the presence of a silver halide solvent. Examples of the silver halide solvent used include U.S. Pat.
No. 3,531,2891, No. 3,574,628, JP-A-54-1019
(A) Organic thioethyls described in JP-A No. 54-158917 and the like; (b) Thiourea described in JP-A Nos. 53-82408, 55-77737, 55-2982, etc. Derivative; JP-A-53-1
(C) Silver halide solvent having a thiocarbonyl group sandwiched between oxygen or sulfur atom and nitrogen atom described in 44319; (d) Imidazoles described in JP-A-54-100717; ) Sulfite; (f) Thiocyanate and the like.

Specific examples of known photographic additives, various couplers and the like which can be used when a color light-sensitive material is constituted by using the silver halide photographic emulsion of the present invention are described below.

[Item] [RD308119] [RD17643]] [RD18716] Color turbidity inhibitor page 1002 page VII-I section 25 page 650 dye image stabilizer page 1001 VII-J section 25 page brightener 998 page V 24 page UV absorber 1003 pages VIII-C and VIII-C pages 25 to 26 Light absorber 1003 pages VIII 25 to 26 Light scattering agents 1003 VIII Filter dyes 1003 pages VIII 25 to 26 binders 1003 pages IX 26 pages 651 pages Antistatic agent 1006 pages XIII 27 pages 650 Hardeners 1004 pages X 26 pages 651 Plasticizers 1006 XII 27 pages 650 Lubricants 1006 XII 27 pages 650 Activators and coating aids 1005 pages XI 26 pages ~ Page 27 Page 650 Matting agent Page 1007 Page XVI Developer (included in the photosensitive material) Page 1011 Item XX-B Item Yellow coupler 1001 Item VII-D Item 25 Page VII-C to G Magenta coupler 1001 Page VII-D Item 25 VII-CG section Cyan coupler page 1001 VII-D section 25 page VII-C to G section Colored coupler 1002 section VII-G section 25 section VII-G DIR coupler 1001 section VII-F section 25 section VII-F section B R coupler page 1002 VII-F Other useful residues page 1001 VII-F release coupler alkali-soluble page 1001 VII-E coupler coupler dispersion method page 1007 section XIV support 1009 page XVII section 28 filter layer page 1002 Item VII-K Auxiliary layer page 1002 Item VII-K layer structure page 1002 Item VII-K Development method page 1010 XIX page 28-29 page 615

[0163]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Emulsion Em-1 >> A seed emulsion (T-1) having two parallel twin planes was prepared by the following method with reference to the description of JP-A-5-34851. Was prepared.

Solution A ossein gelatin 80.0 g potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 0.48 g water 8000 cc solution B silver nitrate 1200 g water 1600 cc solution C ossein gelatin 32.2 g potassium bromide 790 g potassium iodide 70.34 g water 1600 cc solution D ammonia water 470 cc JP-A-62-160128 Using a stirrer, Solution B and Solution C were added to Solution A that was vigorously stirred at 40 ° C. for 7.7 minutes by the double jet method to generate nuclei. During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 35 minutes. Furthermore, the solution D was added in 1 minute, and the aging was continued for 5 minutes. KBr concentration during aging is 0.03 mol / liter,
The ammonia concentration was 0.66 mol / liter.

After completion of the aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, the average grain size was 0.225 μm, and the ratio of double parallel twin planes was 75% in terms of the number of all grains.

Next, using the following seven kinds of solutions, 2
A tabular monodisperse comparative emulsion Em having parallel twin planes
-1 was prepared.

Solution A ₁ ossein gelatin 69.0 g distilled water 3268 cc HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol Solution 2.50cc Seed emulsion (T-1) 71.8g Distilled water to 3500cc.

Solution B ₁ 0.5 N silver nitrate aqueous solution 959.0 cc Solution C ₁ potassium bromide 52.88 g ossein gelatin 35.55 g Distilled water is added to 959 cc.

Solution D ₁ 3.5N silver nitrate aqueous solution 4475.0 cc Solution E ₁ potassium bromide 1863.8 g ossein gelatin 179.0 g Solution 4475 cc with distilled water F ₁ 3% by weight gelatin and silver iodide grains (average grain size 0.05 μm) Fine grain emulsion (preparation method is shown below) 2492.0 g * Aqueous solution containing 7.06 mol silver nitrate and 7.06 mol potassium iodide in 5000 cc of 6.0 wt% gelatin solution containing 0.06 mol potassium iodide 2000 cc of each was added over 10 minutes. The temperature during fine particle formation was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

Solution G ₁ 1.75N aqueous solution of potassium bromide Required amount Solution A ₁ was added to a reaction vessel, and with vigorous stirring, solution B ₁ to solution F ₁ were added by the simultaneous mixing method according to the combination shown in Table 1. Then, seed crystals were grown to prepare a core / shell type silver halide emulsion. However, solution B ₁ ,
114.95 minutes after the addition of C ₁ and F ₁ was started, 10
The pH was adjusted to 7.2 with% potassium hydroxide. As a result, reduction sensitization was performed inside the grains.

Here, (1) solution B ₁ , solution C ₁ and solution F
The addition rate of _1, the addition rate of (2) the solution D ₁ , the solution E ₁ and the solution F ₁ , and the addition rate of (3) the solution D ₁ and the solution E ₁ respectively corresponded to the critical growth rate of silver halide grains. As described above, the addition rate was changed in a function-like manner, and the addition rate was controlled so that small particles other than the growing seed crystal and polydispersion due to Ostwald ripening do not occur.

The temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. pAg
Solution G ₁ was added as needed for control.

Table 1 also shows the amount of silver added at that time and the silver iodide content of the silver halide phase forming the surface with respect to the addition time of the reaction solution.

After grain growth, desalting treatment was carried out according to the method described in Japanese Patent Application No. 4-59351, and then an aqueous gelatin solution was added and redispersed to adjust pH to 5.80 and pAg to 8.06 at 40 ° C.

The silver halide grains contained in the obtained silver halide emulsion were tabular with an average grain size of 1.42 μm (diameter in terms of projected area circle), 85% grains with an average aspect ratio of 3.0 or more, and a grain size distribution of 14.0%. It was a silver halide grain.

[0178]

[Table 1]

<< Preparation of Emulsion Em-2 >> A monodisperse spherical seed emulsion (T-2) was prepared by the following method.

Solution A ₂ Oscein gelatin 80 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% methanol solution 20 cc Make up to 8000 cc with water.

Solution B ₂ Silver nitrate 1200 g Make up to 1600 cc with water.

Solution C ₂ Oscein gelatin 32.2 g Potassium bromide 840 g Water to 1600 cc.

Solution D ₂ Ammonia water 470 cc Solution B ₂ and solution C ₂ were added to the solution A ₂ vigorously stirred at 40 ° C. for 11 minutes by the double jet method to generate nuclei. During this time, pBr was kept at 1.60. Then, the temperature was lowered to 30 ° C. over 12 minutes, and aging was further performed for 18 minutes. Furthermore, the solution D ₂ was added over 1 minute, followed by aging for 5 minutes. The KBr concentration during aging was 0.07 mol / liter, and the ammonia concentration was 0.63 mol / liter.

After completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out by a conventional method to obtain a spherical seed emulsion (T-2). When this seed emulsion was observed with an electron microscope,
It was a spherical emulsion having an average grain size of 0.318 μm and having twin planes.

Next, an emulsion Em-2 was prepared using the following seven kinds of solutions.

Solution A ₃ Oscein gelatin 268.2 g Distilled water 4000 cc Polyisopropylene-polyethyleneoxy-disuccinate ester sodium salt 10% methanol solution 1.5 cc Seed emulsion (T-2) 0.286 mol 28 wt% ammonia solution 528.0 cc 56 wt% acetic acid aqueous solution 795.0 cc A methanol solution containing 0.001 mol of iodine 50.0 cc Make 5930.0 cc with distilled water.

Solution B ₃ 3.5N ammoniacal silver nitrate aqueous solution (pH adjusted to 9.0 with ammonium nitrate) Solution C ₃ 3.5N potassium bromide aqueous solution containing 4.0% by weight gelatin D ₃ 3% by weight gelatin and iodine Fine grain emulsion consisting of silver halide grains (average grain size: 0.05 μm) 0.844 mol * The preparation method is shown below.

6.0% by weight containing 0.06 mol of potassium iodide
To 5000 cc of gelatin solution, 2000 cc of a solution containing 7.06 mol of silver nitrate and 2000 cc of an aqueous solution containing 7.06 mol of potassium iodide.
Added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particle size, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

Solution E ₃ Silver iodobromide grains containing 1 mol% of silver iodide (average particle size 0.04 μm) prepared in the same manner as the above silver iodide fine grain emulsion.
2.20 mol of fine grain emulsion consisting of m) (however, the temperature during fine grain formation was controlled to 3.0 ° C.) Solution F ₃ 1.75N aqueous potassium bromide solution G ₃ 56% by weight acetic acid aqueous solution kept at 70 ° C. in the reaction vessel Solution A ₃ , solution B ₃ , solution C
_{After 3} and the solution D ₃ were added by the simultaneous mixing method over a period of 163 minutes, the solution E ₃ was continuously added at a constant rate for 12 minutes to grow the seed crystal to 1.0 μm.

Here, the addition rates of the solution B ₃ and the solution C ₃ were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, generation of small particles other than the growing seed crystal and Ostwald ripening. Was added at an appropriate addition rate so as not to cause polydispersion. The solution D _{3, that} is, the silver iodide fine grain emulsion is supplied by changing the velocity ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the grain size as shown in Table 2.
A core / shell type silver halide emulsion having a multiple structure was prepared.

Further, by using the solution F ₃ and the solution G ₃ , pAg and pH during crystal growth were controlled as shown in Table 2.
The pAg and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method. After particle formation, JP-A-5-3485
After desalting according to the method described in No. 1, gelatin was added and redispersed to adjust pH to 5.80 and pAg to 8.06 at 40 ° C.

The obtained emulsion grains were observed with an electron microscope. As a result, the twin grains were composed of 100% twin grains and had an aspect ratio of 1.2 to 1.6 with two or more parallel twin planes. It was composed of slightly distorted octahedral twin monodisperse grains having a size of 10% and an average grain size of 1.0 μm.

[0193]

[Table 2]

Emulsions A to J were prepared by the methods described below. The optimum ripening time depends on each emulsion (fog
-Sensitivity evaluation gave the best results). The amount of various additives (sodium thiosulfate, sensitizing dye, chloroauric acid, ammonium thiocyanate) added is in the range of 0.75 to 1.25 times the amount used when preparing the comparative emulsion, and the optimum amount for each emulsion is selected. Was added.

<< Preparation of Comparative Emulsion A >> A part of Emulsion Em-1 was dissolved by heating at 50 ° C. and pH was adjusted to 5.80, and then 52.6 mg of sensitizing dye (sd-1) per mol of silver halide. ,
65.77 mg of (sd-2) and 85.5 mg of (sd-3) were added. 20 minutes after the addition of the sensitizing dye, 5 × 10 ⁻⁶ mol of sodium thiosulfate pentahydrate was added per mol of silver halide,
Then, 1.42 × 10 ⁻⁶ mol of chloroauric acid and 3.15 × 10 ⁻⁴ mol of ammonium thiocyanate were added and the mixture was aged for an appropriate time.

At the end of aging, a stabilizer (ST-1) was added,
Emulsion A was obtained by cooling and solidifying.

ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene

[0198]

Embedded image

<< Preparation of Emulsions B to J >> Emulsions Em-1 and E
Using m-2, Emulsions B to J were prepared by combining the compounds of the present invention with selenium or tellurium sensitization as shown in Table 3.

The compound of the general formula (I) of the present invention was added 10 minutes after the addition of the sensitizing dye in an amount of 3 × 10 ^-3 mol per mol of silver halide as a solution of fluorinated alcohol. Selenium sensitization or tellurium sensitization is carried out by adding triphenylphosphine selenide in an amount of 1,1 × 10 ^-6 mol per mol of silver halide after the addition of sodium thiosulfate.
Also, dibutyl i-propylphosphine telluride was added in the same amount of 8 × 10 ⁻⁷ mol.

The ripening time of each emulsion was set after the start of ripening and before the increase in sensitivity approached saturation and before the rapid increase in fog increased, and the optimum time was set in advance.

[0202]

[Table 3]

Preparation of Single Emulsion Layer Coating Samples 101 to 110 Emulsions A to J obtained as described above were coated according to the following coating formulation.
Coated samples 101 to 110 were prepared by sequentially coating and drying on a triacetyl cellulose film support subjected to an undercoating process.

<Coating Formulation> First layer: green-sensitive silver halide emulsion layer Emulsion (shown in Table 2) 2.5 g / m ² magenta coupler (m-1) 0.01 mol / mol Ag colored magenta coupler (cm-1) 0.005 Mol / mol Ag DIR compound (d-1) 0.0002 mol / mol Ag high boiling solvent (TCP) 0.22 g / m ² Second layer: yellow filter layer Yellow colloidal silver Stain inhibitor (AS-1) emulsion dispersion Hard Membrane agent (HI) TCP: tricresyl phosphate AS-1: 2,5-di-t-octylhydroquinone H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium salt

[0205]

[Chemical 38]

<Evaluation of Sensitometry> The coated samples 101 to 110 obtained as described above were exposed to green light for 1/250 seconds.
After the step wedge exposure of 3.2 CMS, the characteristic curve is obtained by processing in the following processing steps, and the relative sensitivity (fog density +0.15
The reciprocal of the exposure dose that gives the density of, and the relative value with sample 101 being 100) was obtained.

Processing step (38 ° C.) Color development (2 minutes 50 seconds) → bleaching (6 minutes 30 seconds) → washing (3 minutes
15 seconds) -fixing (6 minutes 30 seconds) -washing (3 minutes 15 seconds) -stabilization (1 minute 30 seconds) -drying The composition of the processing liquid used in each processing step is as follows.

Color developer 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.0.

Bleaching liquid Ethylenediaminetetraacetic acid ammonium ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter and pH was adjusted with ammonia water.
Adjust to = 6.0.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

Stabilizer Formalin (37% aqueous solution) 1.5 cc. Conidax (Konica Corporation) 7.5 cc. Add water to make 1 liter.

<Evaluation of Latent Image Stability> Two sets of Samples 101 to 110 were prepared and subjected to wedge exposure using green light.
Store for 4 days under the temperature and humidity conditions of 40 ℃ and 55% RH, and use the remaining 1
The set was stored at −20 ° C. as a control, and the same development processing as above was performed to evaluate the latent image stability. The latent image stability is calculated from the characteristic curve for each sample by the fog density +
The reciprocal of the exposure dose giving a density of 0.15 was determined as the sensitivity, and the sensitivity of each control sample was set to 100, and the relative value was evaluated. The larger the value, the better the latent image stability.

<Evaluation of Illuminance Failure Characteristic> The same evaluation was performed except that the exposure condition in the sensitometric evaluation was changed to 1 / 10,000 seconds and 3.2 CMS, and relative sensitivity was set to 100 for 1/250 second exposure, respectively. Indicated by. The higher the value, the better the illumination failure.

Table 4 shows the relative sensitivity of green color, fog, latent image stability and illuminance failure characteristics.

[0215]

[Table 4]

As is clear from Table 4, all the samples of the present invention have high sensitivity, low fog, excellent latent image stability, and improved illuminance failure characteristics.

Example 2 The compound of the general formula (II) of the present invention was evaluated by the same method as in Example 1. Emulsion C, D, E, G of Example 1
Emulsions K, L, M, N, O and P corresponding to I and J were prepared.

[0218]

[Table 5]

Single emulsion layer coated sample 201 as in Example 1
~ 206 were produced and evaluated in the same manner.

The results are shown in Table 6.

[0221]

[Table 6]

Instead of the compound of the general formula (I), the compound of the general formula (I
It can be seen that good results are obtained even if the compound of I) is chemically sensitized.

Example 3 Studies were conducted to introduce dislocation lines into silver halide grains.

(Preparation of seed crystal emulsion α) JP-A-63-151618
U.S. Pat. No. 4,797,354, West German Patent 3,707,135-A
Referring to No. 1, a silver iodobromide tabular silver halide seed crystal emulsion α having the following double structure was prepared.

Core: 13% of the total seed crystal amount, shell: 87% of the total seed crystal amount, thiourea dioxide was 5 per total seed crystal silver.
After shell formation in the presence of × 10 ^-6 mol / mol Ag,
Compound A is 2 × 10 ⁻⁴ mol / mol Ag with respect to the total seed crystal silver
Add and ripen for 5 minutes.

Compound A: Sodium ethanethiosulfonate << Preparation of Emulsion EM-1 >> Seed crystal emulsion α (silver
170 g in terms of AgNO _{3 and} 40 g of gelatin were included), and the 1-1a solution and the 1-1b solution were simultaneously added over 5 minutes while stirring.

Solution 1-1a Silver nitrate 8 g Water 200 cc Solution 1-1b Potassium iodide 6 g Water 200 cc Next, solutions 1-2a and 1-2b were simultaneously added over 30 minutes while keeping pAg at 9.0.

1-2a liquid silver nitrate 70g water 300cc 1-2b liquid potassium bromide 49g water 300cc After this, desalting was carried out according to a conventional method, gelatin was added, and chloroauric acid and sodium thiosulfate were used to optimize the amount of gold. Sulfur sensitized. This silver halide emulsion is designated as emulsion EM-1.

(Preparation of EM-2) In the particle formation of EM-1, solution 1-1b was replaced with solution 2-1b and solution 1-2b was replaced with solution 2-2b in the same manner as EM-1. Particle formation was performed.

[0230] 2-1b liquid Likewise after grain formation and potassium bromide 5g Potassium iodide 0.6g Water 200 cc 2-2b solution Potassium 4.4g Potassium iodide bromide 5.4g Water 300 cc EM-1, desalting and chemical sensitization I went. This silver halide emulsion is designated as EM-2. EM-1
Table 7 gives an overview of EM-2 and EM-2.

[0231]

[Table 7]

Regarding the above emulsions EM-1 and EM-2,
Chemical sensitization was performed in the same manner as in Example 1 by combining with the compound of the present invention to obtain emulsions a to j.

[0233]

[Table 8]

Using emulsions a to j, single emulsion layer coating samples 301 to 310 were prepared in the same manner as in Example 1 and the same evaluation was carried out. The results are shown in Table 9.

[0235]

[Table 9]

Chemical sensitization was carried out using the compound of the present invention,
In addition, all the samples sensitized with selenium show good results, but among them, a sample using a silver halide emulsion in which 50% or more of all grains have 10 or more dislocation lines per grain 30
5 is especially good.

Example 4 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material sample including the following layers was prepared and designated as Sample 401. The amount of the additive used is the amount expressed in g / m ² unit in terms of silver per 1 m ² of the light-sensitive material for silver halide and colloidal silver, and for the sensitizing dye, the halogenation in the same layer. The number of moles per mole of silver is
For other additives such as couplers, the amounts are shown in units of g / m ² per 1 m ² of the light-sensitive material.

First layer: antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.2
0 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: Low sensitivity red sensitive layer Silver iodobromide emulsion IA 0.15 Silver iodobromide emulsion IB 0.35 Sensitizing dye (SD-1) 2.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.4 × 10 ⁻⁵ Sensitizing dye Dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer : Medium sensitivity red sensitive layer Silver iodobromide emulsion IB 0.30 Silver iodobromide emulsion IC 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 Sensitizing dye (SD-2) 0.86 × 10 ^-4 Sensitizing dye ( SD-3) 1.15 × 10 ^-5 Sensitizing dye (SD-4) 0.86 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 D IR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Seratin 0.79 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion ID 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 sensitization Dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion IA 0.12 Silver iodobromide emulsion IB 0.38 Increase Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 8th layer: Intermediate layer Gelatin 0.41 9th layer: Sensitivity Green-Sensitive Layer Silver iodobromide emulsion IB 0.30 iodobromide emulsion IC 0.34 Sensitizing dye (SD-6) 1.2 × 10 -4 Sensitizing dye (SD-7) 1.2 × 10 -4 Sensitizing dye (SD- 8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point Solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: High sensitivity green sensitive layer Emulsion ID 0.95 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion IA 0.12 Silver iodobromide emulsion IB 0.24 Silver iodobromide emulsion IC 0.12 Sensitization Dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: High sensitivity blue sensitive layer Silver iodobromide emulsion IC 0.15 Silver iodobromide emulsion IE 0.80 Sensitizing dye (SD-9) 8.0x 10 ⁻⁵ Sensitizing dye (SD-11) 3.1 × 10 ⁻⁵ Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion IF 0.40 Ultraviolet absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl Methacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Surfactant (Su -3) Surfactant (Su-4) Gelatin 0.55 In addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, a viscosity modifier, a hardener H-1, H-2. , Stabilizer ST-1, antifoggant AF-1, average molecular weight = 10,000
And two AF-2s with an average molecular weight = 1,100,000 and the preservative DI-1.

The emulsions used for the above samples have internal reduction sensitization, surface high iodine type core / shell structure and IF uniform structure as shown in Table 10. The average particle size is shown as a particle size converted into a cube. Further, each emulsion was optimally sensitized with selenium and gold and sulfur in the same manner as the emulsion H of Example 1.

[0240]

[Table 10]

Su-1: Dioctyl sulfosuccinate sodium salt Su-2: Sodium tri-i-propylnaphthalenesulfonate H-2: Bis (vinylsulfonylmethyl) ether AF-1: 1-phenyl-5-mercaptotetrazole AF-2: poly-N-vinylpyrrolidone OIL-1: dioctyl phthalate OIL-2: tricresyl phosphate OIL-3: dibutyl phthalate SC-1: 2-methyl-5-sec-octadecyl hydroquinone

[0242]

[Chemical Formula 39]

[0243]

[Chemical 40]

[0244]

Embedded image

[0245]

Embedded image

[0246]

[Chemical 43]

[0247]

[Chemical 44]

[0248]

Embedded image

[0249]

Embedded image

Emulsion IB, IC, I
For D and IE, referring to the emulsion layer I of Example 1, emulsions IIB, IIC and I chemically sensitized with the compound I-60 of the present invention were used.
A sample 402 was prepared in the same manner except that ID and IIE were used.

Emulsion I chemically sensitized with III-3 in the same manner
A sample 403 using IIB, IIIC, IIID, and IIIE was prepared.

Samples 401 to 403 were subjected to step wedge exposure using white light, and sensitometry was evaluated through the same development processing steps as in Example 1. Latent image stability and illuminance failure characteristics were also evaluated in the same manner as in Example 1. Table of results
See Figure 11.

[0253]

[Table 11]

As is apparent from the table, the effect of the present invention is remarkable also in the multilayer color light-sensitive material.

[0255]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having high sensitivity, excellent latent image stability, and improved illuminance failure characteristics.

Claims (9)

[Claims] 1. A method for chemically sensitizing a silver halide photographic emulsion, which comprises using at least one compound represented by the following general formula (I). Embedded image [In the formula, R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, and Y represents 5 to 5 together with a nitrogen atom.
It represents a group of non-metal atoms necessary for forming an 8-membered heterocycle. ] 2. A method for chemically sensitizing a silver halide photographic emulsion, which comprises using at least one compound represented by the following general formula (II). Embedded image [In the formula, R ₁₆ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group or -Si (R ₁₇ ) (R ₁₈ ).
Represents (R ₁₉ ). Here, R ₁₇ , R ₁₈ and R ₁₉ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group or an aryloxy group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an acylamino group, a sulfonamide group or an alkylamino group. , An alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom or a —OR ₂₀ group. Here, R ₂₀ represents a group having the same meaning as R ₁₆ . Also, R ₁₆
And R ₁₁ , R ₁₁ and R ₁₂ or R ₁₂ and R ₁₃ are bonded to each other to form 5
A member ring, a 6-membered ring or a spiro ring may be formed. ] 3. The halogenation according to claim 1, wherein the silver halide grains having an aspect ratio of 2 or more chemically sensitize the emulsion in which 50% or more of the projected area of all the silver halide grains is present. Chemical sensitization method of silver photographic emulsion. 4. The chemical sensitization is carried out in the presence of a sensitizing dye or a nitrogen-containing heterocyclic compound.
A silver halide emulsion for photography as described in. 5. The silver halide emulsion to be chemically sensitized is previously reduction sensitized.
The method for chemically sensitizing a photographic silver halide emulsion according to any one of 1. 6. The chemical sensitization of the photographic silver halide emulsion according to claim 1, wherein the chemical sensitization is at least one of selenium sensitization and tellurium sensitization. Method. 7. A silver halide emulsion is 50% of the total number of grains.
7. The chemical sensitization method for photographic silver halide emulsions according to claim 1, wherein the above has 10 or more dislocation lines per grain. 8. A chemical sensitization of a silver halide emulsion in which 50% or more of all grains have 10 or more dislocation lines per grain, using at least one compound represented by the following general formula (III). A method for chemically sensitizing a silver halide photographic emulsion, which comprises: Embedded image [In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group,
It represents an acylamino group, a sulfonamide group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom or an alkoxy group. However, not all of R _{21 to} R ₂₅ are hydrogen atoms. Further, any two adjacent R _{21 to} R ₂₅ may combine with each other to form a 5-membered ring, a 6-membered ring or a spiro ring. ] 9. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion chemically sensitized by the chemical sensitization method according to claim 1.