JPH09197606A - Halogenated silver photographic emulsion and color photographic material using this halogenated silver photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the sensitivity and moisture resistance by having two or more of phase at a different silver iodide content inside of halogenated silver grains, which is included in the emulsion, and spectral-sensitizing this halogenated silver grains with a specified sensitizing pigment. SOLUTION: 50% or more of the whole projection area of the halogenated silver grains, which is included in the emulsion, is formed of flat plate-shaped grains, which has two or more of phase at a different silver iodide content inside of the grains and of which silver iodide content of the maximum silver iodide included phase exists in a range at 5-10% by mole. The halogenated silver grains at 10% by mole of silver iodide content of the surface of the halogenated silver grains is spectral-sensitized by one kind of the sensitizing pigment, which is expressed with a formula. In the formula, R11 means styhoethyl group, R12 means substituent or non-substituent alkyl group, R13 means hydrogen atom or the like, and Z12 means substituent or non- substituent atom group to be required for forming a benzoxazole nucleus or the like, and X1 means a pair of charge balanced ion, and n1 means a numeric for adjusting the load of the whole of a molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic emulsion and a light-sensitive material having improved sensitivity and moisture resistance.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for photographic silver halide emulsions. For example, an extremely high level of performance such as high sensitivity, excellent graininess, and excellent pressure resistance has been demanded. .

A technique for increasing the sensitivity of a silver halide emulsion is as follows.
That is, the sensitization technique relates to a method for producing a silver halide emulsion, relates to a chemical sensitization technique for a silver halide emulsion, relates to a method for spectral sensitization of a silver halide emulsion, a method for designing a silver halide photosensitive material, Various methods are known, such as those relating to the process of developing a silver halide light-sensitive material. Among them, the most preferable and essential method is to increase the photosensitive quantum efficiency of silver halide grains themselves.

For example, a technique using a core having a high silver iodide content inside a grain is known as the most popular technique for improving the quantum efficiency itself of the sensitivity of silver halide grains. A technique for providing a core having a high content is disclosed in JP-A-63-92942.

In recent years, demands for higher sensitivity and higher image quality have been increasingly intensified, and the use of silver halide grains having such a high iodine core phase has been required not only in high-sensitivity photosensitive materials but also in common color negative photosensitive materials. Was also mandatory.

However, the grains having such an internal high iodine core have a drawback that the pressure desensitization is remarkable, which is a serious problem in handling a photographic material using such silver halide grains. I have. If the silver iodide content of the internal high iodine core phase is reduced, the pressure desensitization is improved, but the photographic sensitivity is lowered, and it cannot be put to practical use. Further, when tabular grains are used, the pressure resistance tends to be further deteriorated due to the shape factor. Therefore, development of a silver halide emulsion having high sensitivity and improved pressure desensitization has been desired.

As a means for reducing the silver iodide content of the inner core phase and improving the pressure desensitization while achieving high sensitivity,
It is known to use tabular grains that achieve high sensitivity by increasing the light receiving efficiency per grain of silver halide. For tabular silver halide grains,
Already U.S. Pat. Nos. 4,434,226 and 4,439,
No. 520, No. 4,414, 310, No. 4,433, 0
No. 48, No. 4,414, 306, No. 4, 459, 35
3, JP-A-58-111935 and JP-A-58-11119.
36, 58-11937, 58-11392.
No. 7, 59-99433 and the like.

In Japanese Patent Application No. 6-312075, the maximum silver iodide content inside the grain is less than 8 mol%, a phase having a smaller silver iodide content is present outside the grain, and a dislocation line is formed. An emulsion having high sensitivity and improved pressure desensitization is disclosed by using an emulsion containing five or more silver halide grains.

By the way, when tabular grains, particularly tabular grains having a high aspect ratio, are used, it is necessary to add a large amount of spectral sensitizing dye as the surface area per grain increases. For this reason, the problem that the sensitizing dye contained in the silver halide photographic light-sensitive material is not completely eluted during the development process and remains colored in the light-sensitive material is becoming a serious problem. When the degree of this residual color becomes severe, the linear correlation between the density of the negative film after development and the actual exposure amount is lost, so that the color reproducibility during printing is significantly impaired. In addition, the concentration of residual dye stain generated tends to fluctuate depending on the storage condition of individual samples and the conditions during development.
If the absolute value of the stain density is large, the fluctuation range also becomes large. Therefore, the color reproducibility cannot be maintained only by changing the level setting at the time of printing. Conventionally, a sensitizing dye having a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group in order to improve residual dye stain (for example, JP-A 1-1474).
51, JP-A-61-294429, JP-B-45-3
No. 2749, JP-A-61-77843) has been studied. However, when the hydrophilicity of the sensitizing dye is increased, the adsorption force generally becomes weak, so that the storability is deteriorated and the residual color, sensitivity and storability are accompanied. In terms of compatibility of both, sufficient effect was not obtained.

[0010]

The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide emulsion having improved sensitivity and moisture resistance and a photographic light-sensitive material using the same.

[0011]

As a result of earnest research, the present inventors have found that the object of the present invention can be achieved by the following technique.

(1) 50% or more of the total projected area of the silver halide grains contained in the emulsion has two or more phases having different silver iodide contents inside the grains, and the maximum iodine inside the grains is The silver iodide content of the silver halide-containing phase is more than 5 mol% and 10 mol%
The silver halide grains having tabular grains of less than 10% and having a silver iodide content of 10 mol% or more on the surface of the silver halide grains are represented by the following general formula [I], general formula [II] or general formula [II]. II
A silver halide photographic emulsion characterized by being spectrally sensitized with at least one sensitizing dye represented by the formula I).

[0013]

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In the formula, R ₁₁ represents a sulfoethyl group,
R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ each represent a substituent selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and R
₁₃ , R ₂₃ and R ₃₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
Z ₁₂ and Z ₃₁ represent an atomic group necessary for forming a substituted or unsubstituted benzoxazole nucleus or naphthoxazole nucleus, and Z ₃₂ represents a substituted or unsubstituted benzothiazole nucleus, naphthothiazole nucleus, substituted or unsubstituted Represents an atomic group necessary for forming any of the benzoselenazole nucleus and the naphthoselenazole nucleus. X ₁ , X ₂ and X ₃ represent charge balancing counterions, and n 1, n 2 and n 3 represent numerical values for controlling the charge of the whole molecule.

(2) At least 50% of the total projected area of silver halide grains contained in the emulsion has two or more phases having different silver iodide contents inside the grains, and the maximum silver iodide content is contained. The silver iodide content of the phase is more than 5 mol% and less than 10 mol%, the silver iodide content on the surface of the silver halide grain is 10 mol% or more, and the dislocation line is inside the silver halide grain. A tabular grain containing the silver halide grain, which is spectrally sensitized with at least one sensitizing dye represented by the general formula [I], the general formula [II] or the general formula [III]. A silver halide photographic emulsion characterized in that

(3) The silver halide photographic emulsion according to (1) or (2), wherein the silver halide grains are sensitized with selenium.

(4) The silver halide grain according to (1), (2) or (3), characterized in that the silver halide grain is a grain formed by using at least a part of fine silver halide grains. Photographic emulsion.

(5) The silver halide photographic emulsion according to (4), wherein the fine silver halide grains have a solubility lower than that of the host grains under the grain forming conditions.

(6) At least one photosensitive silver halide emulsion layer is provided on a support, and (1), (2), (3), (4) or in at least one emulsion layer. A silver halide color photographic light-sensitive material containing the silver halide emulsion described in (5).

(7) At least one photosensitive silver halide emulsion layer is provided on a support, and (1), (2), (3), (4) or at least one emulsion layer is contained in the emulsion layer. At least 1 represented by the following general formula [IV] is contained in the emulsion layer or in another hydrophilic colloid layer having a water permeability to the layer, which contains the silver halide emulsion described in (5). A silver halide color photographic light-sensitive material characterized by containing various compounds.

In the general formula [IV] Het- (SR) _i , Het represents a heterocycle, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. i
Represents an integer of 0, 1 or 2. However, Het or R is-
It directly or indirectly has at least one group selected from SO ₃ H, —COOH or —OH or a salt thereof.

The details will be described below.

In the present invention, the tabular (like) grain is defined by a circle having two parallel principal planes and having a circle equivalent diameter (diameter of a circle having the same projected area as the principal plane) and a principal plane. Ratio of distance (ie grain thickness), ie aspect ratio 2
The above particles are said.

At least 50% of the total projected area of all the tabular grains of the present invention is preferably tabular grains having an aspect ratio of 5 or more, more preferably 8 or more.

The diameter of the tabular grains of the present invention is 0.3 to 1
0 μm, preferably 0.5 to 5.0 μm, more preferably 0.5 to 2.0 μm. The particle thickness is preferably from 0.05 to 0.8 μm.

The particle diameter and particle thickness in the present invention can be measured by the method described in US Pat. No. 4,434,226.

The size distribution of the tabular grains of the present invention is the coefficient of variation of the circle-converted diameter of the principal plane (the diameter of a circle having the same projected area as the principal plane) (the standard deviation of the diameter distribution divided by the average diameter). ) Is preferably 30% or less, and 20%
It is more preferred that:

The halogen composition of the silver halide grains is preferably silver iodobromide or silver chloroiodobromide, and the silver iodide content is preferably 1 to 15 mol%.
It is more preferably ˜12 mol%.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is the variation coefficient of the silver iodide content (the standard deviation of the silver iodide content intergrain distribution is the average silver iodide content. It is preferably 30% or less, more preferably 20% or less.

The tabular grain of the present invention has at least two phases having different halogen compositions inside the grain, and the silver iodide content of the phase having the maximum silver iodide content excluding the outermost layer has a silver iodide content of 10 or more. It is less than mol%, preferably less than 8 mol%. The volume fraction of the phase in the particles is preferably 30% or more and 90% or less, and more preferably 30% or more and 60% or less.

The structure relating to the halogen composition in the grain is X
It can be examined by a line diffraction method, a composition analysis method using EPMA, or the like.

The term "silver iodide content on the surface of silver halide grains" as used in the present invention means a value determined by the following method. The silver iodide content on the grain surface is measured by the XPS method (X-r
ayPhotoelectron Spectrosc
(opy: X-ray photoelectron spectroscopy). The sample was cooled to -115 ° C or less in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and Mg was used as a probe X-ray.
Kα is irradiated with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and measurement is performed for Ag3d5 / 2, Br3d, and I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by the sensitivity factor (Sensitivity Factor),
The silver iodide content on the surface is obtained from these intensity ratios.

The term "maximum silver iodide-containing phase in the grain" as used in the present invention does not include a high iodine localized region produced by the operation described below for forming dislocation lines.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, JP-A Nos. 61-6643, 61-146305 and 62
-157024, 62-18556, 63-9
No. 2942, No. 151618, No. 63-163451
Nos. 63-220238 and 63-31244 can be referred to. For example,
One of the simultaneous mixing method, the double jet method and the simultaneous mixing method, which is a so-called control double jet method for keeping the pAg in the liquid phase where silver halide is formed constant, and soluble silver halides having different compositions A triple jet method of adding can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. As a silver halide solvent often used,
Ammonia, thioethers and thioureas can be mentioned. Regarding thioethers, U.S. Pat.
No. 1,157, No. 3,790,387, No. 3,5
No. 74,628 can be referred to. Further, the mixing method is not particularly limited, and a neutral method without using ammonia, an ammonia method, an acidic method, or the like can be used. However, from the viewpoint of reducing fogging of silver halide grains, it is preferably pH (hydrogen). (Logarithm of reciprocal of ion concentration)
It is 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention contain iodide ions. In this case, the method of adding iodide ions in grain growth is not particularly limited and they may be added as an ionic solution such as potassium iodide. Further, it may be added as fine silver iodide grains.

In the silver halide emulsion of the present invention, when at least a part of the silver halide emulsion is formed by using fine silver halide grains, the halogen composition distribution between grains becomes more uniform and the non-uniformity of the photosensitive quantum efficiency is reduced. Is preferable, and it is more preferable to grow by using silver halide fine grains throughout the grain growth. However, in the present invention, the phrase "grow with silver halide fine particles throughout the grain" does not include the seed grain when the seed grain is used.

Grain formation using silver halide fine grains is as follows.
Grain growth may be carried out using only silver halide fine grains in the same manner as the grains disclosed in JP-A-1-183417, 1-183644, 1-183645 and the like.
What is necessary is just to supply at least one of the halogen elements by silver halide fine particles. In this case, the iodide ions are preferably supplied by silver halide fine particles. As in the claims of Japanese Patent Application No. 3-218608, the number of silver halide fine grains used for grain growth is two or more, and at least one of them is composed of only one halogen element. Good.

As in the claims of JP-A-2-167537, it is desirable to use silver halide grains having a solubility lower than that of the growing silver halide grains, and as the silver halide grains having a low solubility product. It is particularly desirable to use silver iodide.

The dislocations of tabular grains are described in, for example, J. F. Ham
ilton, Photo. Sci. Eng. , 11 (1
967), 57 and T.M. Shiozawa, J .; Sci.
Photo. Sci. Japan, 35 (1972), 2
The observation can be performed by the method described in No. 13, that is, a direct method using a transmission electron microscope at a low temperature. That is,
The silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for an electron microscope, and the sample is placed in a manner to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, the use of a high-pressure electron microscope (200 kV for a thickness of 0.25 μm) enables more clear observation. From the grain photograph obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The dislocation position of the grain of the present invention is not particularly required to be at a specific position, but it is preferable that it is present at the fringe portion of the tabular grain. It is also preferable that it exists both in the fringe portion of the particle and inside the particle.

The fringe portion of the tabular grain referred to in the present invention refers to the outer periphery of the tabular grain, and more specifically, the perpendicular line drawn from the center of gravity of the tabular grain projection surface viewed from the main plane side to each side of the grain is the perpendicular line. The area outside 50% (side) of the length, preferably outside 70%, and more preferably outside 80%.

The dislocation line inside the grain referred to in the present invention means a dislocation line existing in a region other than the above-mentioned fringe portion.

The number of dislocations in the tabular grains of the present invention is 5
Grains containing more than one dislocation preferably account for 50% or more of the total projected area of silver halide grains in the emulsion, and 80%
It is more preferable that the above is satisfied. The number of dislocations is 1
It is more preferable that the number is 0 or more.

When there are dislocation lines inside the grain and the fringe portion, it is preferable that there are 5 or more dislocation lines inside the grain, and it is more preferable that there are 5 or more dislocation lines both inside the fringe portion and inside the grain.

The method of introducing the dislocation lines of the present invention is not particularly limited, but a method of adding an aqueous solution of an iodine ion such as potassium iodide and a water-soluble silver salt solution by a double jet at a position where the dislocation is desired to be introduced, or iodine. A method of adding fine silver halide grains, a method of adding only an iodine ion solution, JP-A-6-
The method can be carried out by a method using an iodide ion releasing agent as described in No. 11781. A method of adding an aqueous iodide ion solution and a water-soluble silver salt solution by a double jet,
A method of adding fine silver iodide grains and a method of using an iodide ion releasing agent are preferable, and a method of using fine silver iodide grains is more preferable. The aqueous solution of iodide ions is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate.

The dislocation is introduced preferably after the formation of the maximum silver iodide-containing phase inside the grain, more preferably after the formation of the phase and before the formation of the adjacent phase.

Further, in relation to the position of the whole grain, it is preferably introduced in a proportion of 50 to 95% of the silver amount in the whole grain, and more preferably 60 to less than 80%.

The silver halide emulsion of the present invention can be subjected to reduction sensitization. Reduction sensitization is performed by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, a silver halide emulsion or a mixed solution for grain growth is prepared under a low pAg of pAg7 or less, or
It is carried out by ripening or growing particles under a high pH condition of H7 or higher. You may perform combining these methods.

Further, reduction sensitization may be carried out before or after the chemical sensitization step as shown in JP-A-7-219093 and JP-A-7-225438.

Further, reduction sensitization may be carried out in the presence of the oxidizing agent shown below. In particular, the compounds described below, formulas (1) to
It is preferable to carry out reduction sensitization in the presence of (3).

Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salt. Other suitable reducing agents include borane compounds,
Examples thereof include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 ^-2 per mol of silver halide.
Preferred is from 10 to 10 ^-8 mol.

A silver salt can be added for low pAg ripening, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3 (where pAg = -log [Ag ⁺ ]).

The high pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate for silver halide formation, an alkaline compound excluding ammonia is preferably used because the effect of ammonia is reduced.

As a method for adding the silver salt or the alkaline compound for reduction sensitization, rush addition may be performed, or addition may be performed over a certain period of time. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide.

Further, it may be added separately from the soluble silver salt and the soluble halide.

In the present invention, as a method of reducing and sensitizing the inside of grains, in the form of growing crystals from seed grains,
It is preferable that the low pAg ripening is carried out after the seed emulsion is formed, that is, immediately before the desalting of the seed grains to after the desalting, by adding silver nitrate for ripening. In particular, it is preferable to add silver nitrate and ripen the seed particles after desalting, and the ripening temperature is preferably 40 ° C. or more and 50 ° C. to 80 ° C. The aging time is preferably 30 minutes or more and 50 to 150 minutes.

In the form of growing from seed particles, high p
When performing H ripening, the volume of the particles after growth is 7
It is necessary to grow the particles at least once through an environment having a pH of 7 or more before the portion corresponding to 0% grows. Based on the volume of the particles after the growth, the particles grow to pH 7 until the portion corresponding to 50% grows. More preferably, the particles are grown at least once through the above environment, and p is required until a portion corresponding to 40% of the volume of the grown particles grows.
It is particularly preferable that the particles grow at least once through an environment of H8 or higher.

The silver halide emulsion of the present invention may contain an oxidizing agent for silver during the production process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound which converts silver atoms by-produced in the process of forming silver halide grains into silver ions is effective. Here, the generated silver ions may form a water-insoluble silver salt such as silver halide, silver sulfide, or silver selenide, or form a water-soluble silver salt such as silver nitrate. May be.

Even if the oxidizing agent for silver is an inorganic substance,
It may be an organic substance. As the inorganic oxidizing agent, ozone, hydrogen peroxide and its adduct (for example, NaBO _{2.
H 2 O 2 · 3H 2 O} , 2NaCO 3 · 3H 2 O 2, Na 4 P 2 O
_{7 · 2H 2 O 2, 2Na} 2 SO 4 · H 2 O 2 · H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 4 P
₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti
_{(O 2) C 2 O 4} ] · 3H 2 O, 4K 2 SO 4 · Ti (O 2)
_{OH · SO 4 · 2H 2 O} , Na 3 [VO (O 2) (C 2 O 4)
₂ · 6H ₂ O]), permanganate (e.g. KMn
O _4), an oxyacid salt such as chromate (e.g., K ₂ Cr ₂ O _7), a halogen element such as iodine and bromine, perhalogenate (e.g., potassium periodate), the high-valence metal Salts (eg, potassium hexacyanoferrate) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and the like.
Compounds that release an active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B) are mentioned.

Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates and quinones, and particularly preferably the thiols represented by the following formulas (1) to (3). The compound is a sulfonate compound, and the most preferred is a compound represented by the formula (1).

(1) R-SO ₂ S-M (2) R-SO ₂ S-R ₁ (3) RSO ₂ S-L _m -SSO ₂ -R _{2 In the} formula, R, R ₁ and R ₂ are They may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M is a cation, L is a divalent linking group, and m is 0 or 1.

The compounds represented by the formulas (1) to (3) may be polymers containing divalent groups derived from these structures as repeating units, and R, R ₁ , R ₂ , L
May combine with each other to form a ring.

The thiosulfonate compound represented by the formulas (1) to (3) will be described in more detail. When R, R ₁ and R ₂ are aliphatic groups, they are saturated or unsaturated, linear, branched or cyclic aliphatic hydrocarbon groups, preferably having 1 to 2 carbon atoms.
2 alkyl groups (methyl, ethyl, propyl, butyl,
Pentyl, hexyl, octyl, 2-ethylhexyl,
Decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, t-butyl and the like), an alkenyl group having 2 to 22 carbon atoms (such as allyl and butenyl),
And alkynyl groups (propargyl, butynyl, etc.), which may have a substituent.

When R, R ₁ and R ₂ are aromatic groups, they include monocyclic or condensed ring aromatic groups, and preferably have 6 to 6 carbon atoms.
20 and, for example, phenyl and naphthyl. These may have a substituent.

When R, R ₁ and R ₂ are heterocyclic groups, nitrogen,
3 having at least one element selected from oxygen, sulfur, selenium and tellurium and having at least one carbon atom
To 15-membered ring, preferably 3 to 6-membered ring, for example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tetrazole, Examples thereof include triazole, benzotriazole, oxadiazole and thiadiazole rings.

Substituents for R, R ₁ and R ₂ include alkyl groups (eg, methyl, ethyl, hexyl), alkoxy groups (eg, methoxy, ethoxy, octyloxy),
Aryl groups (eg, phenyl, naphthyl, tolyl),
Hydroxy group, halogen atom (for example, fluorine, chlorine,
Bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl, valeryl), sulfonyl group (eg, Methylsulfonyl,
Phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group (eg, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, Examples include an amino group, a —SO ₂ SM group (M represents a monovalent cation), and a —SO ₂ R ₁ group.

The divalent linking group represented by L is C,
An atom or an atomic group containing at least one selected from N, S and O can be mentioned. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group,
-O -, - S -, - NH -, - CO -, - SO 2 - is made of a single or a combination of these, and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. As the divalent aliphatic group, for example,

[0069]

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Examples thereof include a xylylene group. Examples of the divalent aromatic group include a phenylene group and a naphthylene group.

These substituents may be further substituted with the above-mentioned substituents.

M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (eg, ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (eg, tetraphenylphosphonium), and a guanidyl group.

When the compounds represented by formulas (1) to (3) are polymers, examples of the repeating unit include the following. These polymers may be homopolymers or copolymers with other copolymerized monomers.

[0074]

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Specific examples of the compounds represented by the general formulas (1) to (3) include, for example, JP-A-54-1019, British Patent No. 972,211 and Journal of Orga.
nic Chemistry vol. 53, p. 39
6 (1988).

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[0077]

[Chemical 6]

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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The amount of the oxidizing agent added to 1 mol of silver of the present invention is about 10 ^-7 to 10 ^-1 mol, preferably 10 ^-6 to 10 ^-2.
Mol, and more preferably 10 ⁻⁵ to 10 ⁻³ mol. The oxidizing agent is preferably added during grain formation, or before or during formation of a structure due to a difference in halogen composition. Examples of the addition method include a conventional method for adding an additive to a photographic emulsion. For example, a water-soluble compound is made into an aqueous solution having an appropriate concentration, and a compound insoluble or hardly soluble in water is mixed with a suitable organic solvent which is miscible with water. Among them (alcohols, glycols, ketones, esters, amides, etc.), a method of dissolving in a solution which does not adversely affect the photographic properties and adding it as a solution can be adopted.

The silver halide emulsion used in the photographic light-sensitive material of the present invention is preferably sensitized with a selenium compound or a tellurium compound.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. Specific examples of selenium sensitizers and techniques for using them are disclosed in the following patent specifications. That is, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,446, 3,297,447, 3,320,069, No. 3,408,196, No. 3,408,197, No. 3,442,653, No. 3,420,670, No. 3,591,385, No. 52-34491, No. 52- 34492, 53-295, and 57-22.
No. 090, JP-A-59-180536 and JP-A-59-18.
Nos. 5330, 59-181337, 59-187
No. 338, No. 59-192241, No. 60-1500
No. 46, No. 60-151637, No. 61-24673
No. 8, JP-A-3-42221, JP-A-3-24537, JP-A-3-111838, JP-A-3-116132, and JP-A 3-1.
48648, 3-237450, 4-1683.
No. 8, No. 4-25832, No. 4-25832, No. 4
-32831, 4-96059, 4-1092
No. 40, No. 4-140738, No. 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-191729, No. 4-1.
95035, 4-271341, 4-34446.
No. 36, No. 5-11385, No. 5-40324, No. 5-224332, No. 5-224333, No. 6-4.
0324, 6-43576, 6-75328.
No. 6, No. 6-110149, No. 6-175258, No. 6-175259, No. 6-180478, and No. 6-2.
08184, 6-208186, 6-2651
No. 18, No. 6-281642, etc., and the selenium sensitizers and the techniques for using them can be used.

The technique relating to selenium sensitization is described in H. E. FIG.
Journalof Photog by Spencer et al.
raphic Science, Vol. 31, 158-1
It is also disclosed in scientific literature such as page 69 (1983).

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.) , Selenophosphates (for example, tri-p-triselenophosphate, etc.), selenides (diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide). Particularly preferred selenium sensitizers are selenoureas, selenophosphates, and selenides.

The selenium compound (selenium sensitizer) preferably used in the chemical ripening of the silver halide emulsion of the present invention is described below.
The following shows a specific example.

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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The addition amount of the selenium compound varies depending on the compound used, the type of silver halide photographic emulsion, the conditions of chemical ripening, etc., but is usually 10 ^-8 to 10 ^-3 mol per mol of silver halide. And is preferably in the range of 5 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol per mol of silver halide.

Further, the addition method is, depending on the nature of the selenium compound used, a method of dissolving in water or an organic solvent such as methanol, ethanol and ethyl acetate, alone or in a mixed solvent, or by premixing with a gelatin solution and adding. Method,
As disclosed in JP-A-4-140739, it is added at the time of chemical sensitization in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

The value of pAg (logarithm of reciprocal of silver ion concentration) at the time of chemical ripening is preferably 6.0 to 10.0, more preferably 6.5 to 9.5. The pH at the time of chemical aging is preferably 4 to 9, and more preferably 4.0 to 6.5. The temperature during chemical aging is preferably 40 ° C to 90 ° C, more preferably 45 ° C to 85 ° C.
It is.

For chemical ripening of the silver halide emulsion of the present invention, other chemical sensitizers such as sulfur sensitizers and gold sensitizers can be used in combination.

As the sulfur sensitizer, US Pat.
4,944, 2,410,689, 2,27
8,947, 2,728,668, 3,50
Nos. 1,313 and 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-55-450.
16, JP-A-56-24937, JP-A-5-16513.
Sulfur sensitizers described in No. 5 and the like can be used. Specific examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. And the like are preferred examples. The amount of the sulfur sensitizer to be added is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is from 1 × 10 ^-4 mol to 1 × 10 ^-9 per mol of silver halide. Preferably it is molar. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the present invention, it is also preferable to use a gold sensitizer in combination, specifically, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds. The addition amount of the gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is from 1 × 10 ^-4 mol to 1 × 10 ^-9 per mol of silver halide. Preferably it is molar. More preferably, 1 × 10 ⁻⁵ mol to 1 ×
It is 10 ^-8 mol.

In the present invention, it is preferable to use sulfur sensitization and gold sensitization in combination, and the molar ratio of the selenium sensitizer to the sulfur sensitizer and the gold sensitizer is arbitrary, but the selenium sensitizer It is preferable to use a sulfur sensitizer in an equimolar amount or more.

Other chemical sensitizers that can be used in combination include, for example, US Pat. Nos. 2,448,060 and 2,56.
No. 6,245, No. 2,566,263, etc., and salts of noble metals such as platinum, palladium, and rhodium.

The chemical sensitization of the present invention is carried out in the presence of a thiocyanate (eg, ammonium thiocyanate, potassium thiocyanate) or a 4-substituted thiourea (eg, tetramethylthiourea) which is a silver halide solvent. You can also

Next, the following general formulas [I] and [II] of the present invention are described.
And the spectral sensitizing dye represented by [III] will be described.

[0106]

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In the formula, R ₁₁ represents a sulfoethyl group,
R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , and R ₃₂ represent a substituent selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group, and R
₁₃ , R ₂₃ and R ₃₃ represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z
₁₂ , Z ₃₁ represents an atomic group necessary for forming a substituted or unsubstituted benzoxazole nucleus or naphthoxazole nucleus, and Z ₃₂ represents a substituted or unsubstituted benzothiazole nucleus, naphthothiazole nucleus, substituted or unsubstituted It represents a group of atoms necessary for forming either a benzoselenazole nucleus or a naphthoselenazole nucleus. X ₁ , X ₂ and X ₃ represent charge balancing counterions, and n ₁ , n ₂ and n ₃ represent numerical values for controlling the charge of the whole molecule.

Examples of the alkyl group represented by R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ in the general formulas [I], [II] and [III] include a methyl group, an ethyl group and a propyl group. , Isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group and the like, and these alkyl groups are further substituted with the following substituents. May be.

(Examples of Substituents) Alkenyl group: eg, vinyl group, allyl group, etc. Alkynyl group: eg, propargyl group, etc. Aryl group: eg, phenyl group, naphthyl group, etc. Heterocyclic group: eg, pyridyl group, thiazolyl group, oxazolyl group, Imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.Halogen atom: Fluorine atom, chlorine atom, bromine atom, iodine atom Alkoxy group: For example, methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, etc. Aryloxy group: for example, phenoxy group , Naphthyl Oxy group, etc. alkoxycarbonyl group: for example, methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group, etc. aryloxycarbonyl group: for example, phenyloxycarbonyl group, Naphthyloxycarbonyl group, etc. Sulfonamide group: For example, methylsulfonylamino group,
Ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc. Sulfamoyl group: for example aminosulfonyl group , A methylaminosulfonyl group, a dimethylaminosulfonyl group, n
-Butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc. : For example, a methylureide group, an ethylureide group, a pentylureide group, a cyclohexylureide group,
n-octylureido group, n-dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.Acyl group: for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, onyl group, n-pentylcarbonyl group, Cyclohexylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc. Carbamoyl group: For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl Group, propylaminocarbonyl group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, n Dodecyl amino carbonyl group, phenylaminocarbonyl group, naphthyl aminocarbonyl group, 2
Amide group: for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, n-pentylcarbonylamino group, cyclohexylcarbonylamino group, n-octylcarbonylamino group, 2- Ethylhexylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc. Sulfonyl group: for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl Group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc. Amino group: for example, amino group, ethylamino group, dimethylamido Group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.Others, cyano group, nitro group, carboxy group, hydroxy group, In general formulas [I], [II] and [III], R ₁₂ ,
The alkyl group represented by R ₂₁ , R ₂₂ , R ₃₁ , and R ₃₂ is preferably a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms. preferable. Preferably, at least one of R ₂₁ and R ₂₂ and R ₃₁ and R ₃₂ is a substituent selected from a sulfoalkyl group or a carboxyalkyl group.

As the substituted alkyl group represented by R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , and R ₃₂ , JP-A-5-93978 is known.
Alkyl groups containing a substituent dissociating in an alkaline solution described in JP-A No. 6-82948 and the like are also preferably used in the present invention.

Examples of the alkenyl group represented by R ₁₁ and R ₁₂ include a vinyl group and an allyl group, and these alkenyl groups are alkyl groups represented by R ₁₁ and R ₁₂ .
And a substituent similar to those exemplified as the substituent of the alkyl group.

Examples of the alkynyl group represented by R ₁₁ and R ₁₂ include a propargyl group and the like. These alkynyl groups are the alkyl groups represented by R ₁₁ and R ₁₂ , and the substituents exemplified as the substituents of the alkyl group. It can be substituted by a group similar to the group.

Examples of the aryl group represented by R ₁₁ and R ₁₂ include a phenyl group and a naphthyl group. These aryl groups include an alkyl group represented by R ₁₁ and R ₁₂ .
And a substituent similar to those exemplified as the substituent of the alkyl group.

R ₁₃ , R ₂₃ and R ₃₃ represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Particularly, an ethyl group is preferable.

The benzoxazole nucleus or naphthoxazole nucleus represented by Z ₁₂ and Z ₃₁ may have a substituent, and specific examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom). Atoms, etc.), alkyl groups having 6 or less carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc.), aryl groups (eg, phenyl group), alkoxy groups having 4 or less carbon atoms (eg, methoxy group) , Ethoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.),
An acyl group having 6 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, etc.), an alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), hydroxy Group, cyano group, trifluoromethyl group and the like.

The benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus or naphthoselenazole nucleus represented by Z ₃₂ may have a substituent, and specific examples of the substituent include a halogen atom (for example, Chlorine atom, bromine atom, fluorine atom, etc.), alkyl group having 6 or less carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group), 4 or less carbon atoms Alkoxy groups (eg, methoxy group, ethoxy group, butoxy group), aryloxy groups (eg, phenoxy group), acyl groups having 6 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group), 8 or less carbon atoms Alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbo group Group, such as benzyloxycarbonyl group), such as hydroxy group.

(X ₁ ) n1, (X ₂ ) n2 and (X ₃ ) n
3 is included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye. Therefore, n1, n2, and n3 can take an appropriate value of 0 or more as needed. Typical cations are inorganic or organic ammonium ions,
Alkali metal ions, alkaline earth metal ions,
On the other hand, examples of the anion include a halogen anion, a substituted aryl sulfonate ion, an alkylsulfate ion, a thiocyanate ion, a perchlorate ion, and a tetrafluoroborate ion.

The sensitizing dyes used in the present invention are F.I. M.
FM Hamer, "Heterocyclic Compounds-Cyanine Soybean and Relayed Compounds (Heterocycle)
c Compounds-Cyanine Dyes
and Related Compounds) "4th
Chapters, Chapter 5, Chapter 6, pages 86-119, John Wiley and Sons
d Sons) (1964), D.S. M. DM Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry"
lic Compounds-Special Top
icsin Heterocyclic Chemis
try) ", Chapter 8, pp. 482-515, John Wiley and Sons (John Wiley an)
d Sons) (1977) and the like.

General formula [I] used in the present invention is as follows.
Specific examples of the sensitizing dyes represented by [II] and [III] are shown below, but are not limited thereto.

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[0121]

[Chemical 21]

[0122]

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[0124]

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[0125]

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The sensitizing dyes according to the present invention can be used alone, but it is preferable to use two or more kinds of dyes in combination. When two or more kinds of dyes are used in combination, the dye represented by the general formula [I] and the dye represented by the general formula [II], and the dye represented by the general formula [I] and the general formula [II
It is more preferable to combine the dye represented by the formula [I] or the dye represented by the formula [II] with the dye represented by the formula [III]. At least one of the dyes represented by the general formula [I] and at least one of the dyes represented by the general formula [II]
It is a preferable embodiment of the present invention that the combination of the dye and the dye represented by the general formula [III] is used in combination to improve the latent image storability.

The above sensitizing dye can also be used in combination with other sensitizing dyes or supersensitizers. Other cyanine dyes are preferable as the sensitizing dye to be combined with the sensitizing dye according to the present invention.

As supersensitizers to be combined with the sensitizing dyes of the present invention, styryl compounds and hemicyanine compounds described in, for example, JP-A-3-219233 and Japanese Patent Application No. 5-225511 are preferably used.

The addition amount of the sensitizing dye is preferably in the range of 2 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably in the range of 5 × 10 ^{−6 to} 5 × 10 ⁻³ mol, per mol of silver halide. More preferable.

A method well known in the art can be used for adding the sensitizing dye to the emulsion. For example, these sensitizing dyes can be directly dispersed in the emulsion, or dissolved in a water-soluble solvent such as pyridine, ethanol, methyl cellosolve, fluorinated alcohol or a mixture thereof, and the emulsion in the form of a solution thereof is obtained. Can also be added.

Further, the sensitizing dye is described in US Pat. No. 3,469,9.
No. 87, for example, a method in which a dye is dissolved in a volatile organic solvent, this solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion.
As described in No. 5, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion may also be used.

The above-mentioned general formula [I] used in the present invention,
The sensitizing dyes represented by [II] and [III] can be added to the emulsion at any time during the production process from the time when silver halide grains are formed until immediately before coating on a support. Further, it may be added in plural times.

The order of addition of the stabilizer and the antifoggant is not limited, but it is preferably added at the time of grain formation or chemical ripening, that is, before the preparation of the coating solution.

General formulas [I], [II] and [II] according to the present invention
The sensitizing dye represented by the formula I) is not particularly limited as long as it is a photosensitive silver halide emulsion layer, but it is preferable to introduce it into the green-sensitive silver halide emulsion layer. When a plurality of green-sensitive silver halide emulsion layers are provided, the layer to be introduced may be any one of the layers or a plurality of layers. It may also be incorporated in the green-sensitive layer and other constituent layers and / or other color-sensitive layers.

The silver halide emulsion of the present invention preferably contains a compound represented by the following general formula [IV].

[0142] In the general formula [IV] Het- (SR) _i Formula, Het represents a heterocycle, R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group. i represents an integer of 0, 1 or 2. However, Het or R is -SO
_{It has} at least one group selected from ₃ H, —COOH or —OH or a salt thereof directly or indirectly.

The heterocycle represented by Het in the general formula [IV] includes, for example, oxazole ring, imidazole ring, thiazole ring, triazole ring, selenazole ring, tetrazole ring, oxadiazole ring, thiadiazole ring, thiazine ring, It represents a triazine ring, a benzoxazole ring, a benzthiazole ring, a benzimidazole ring, an indolenine ring, a benzselenazole ring, a naphthothiazole ring, a triazaindolizine ring, a diazaindolizine ring, a tetraazaindolizine ring and the like.

Among the compounds represented by the general formula [IV], the compounds represented by the following general formulas [V] and [VI] are more preferable.

[0145]

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In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and j represents an integer of 0 or 1. However, R ¹ or R ² is -S
O with ₃ H, in at least one direct or indirect -COOH or a group, or selected from -OH their salts.

[0147]

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In the formula, R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group,
R ⁴ represents a substituent.

Z ¹ is an oxygen atom, a sulfur atom, or --N
(R ⁵ ) —, wherein R ⁵ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, —N
(R ⁶ ) represents (R ⁷ ). R ⁶ and R ⁷ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. However, R ³ , R ⁴ or R ⁵ is -SO ₃ H, -COO
It has, directly or indirectly, at least one group selected from H or -OH or a salt thereof.

As the cation forming these salts,
Preferably, alkali metal cations (eg, Na ⁺ , K ⁺
Etc.), alkaline earths, metal cations (eg Ca ⁺⁺ , M
g ⁺⁺ ) and ammonium cations (eg, ammonium cation, triethylammonium cation, pyridinium cation, etc.).

In the general formulas [IV], [V] and [VI],
Examples of the alkyl group represented by R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ or R ⁷ include, for example, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, Cyclopentyl, hexyl, cyclohexyl, octyl,
Dodecyl and the like. These alkyl groups further include a halogen atom (eg, chlorine, bromine, fluorine, etc.), an alkoxy group (eg, methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), and an aryloxy group (eg, phenoxy, naphthyl, etc.) Oxy etc.),
An aryl group (eg, phenyl, naphthyl, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl, naphthyloxycarbonyl, etc.), a heterocyclic group ( For example, 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidyl, piperazyl,
Selenazolyl, sulfolanyl, piperidinyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrimidyl, pyrazolyl, furyl, etc., amino group (eg, amino, N, N-dimethylamino, anilino, etc.), hydroxy It may be substituted by a group, a cyano group, a sulfo group, a carboxy group, a sulfonamide group (for example, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ or R
Examples of the alkenyl group represented by ⁷ include vinyl and allyl, examples of the alkynyl group include propargyl, examples of the aryl group include phenyl and naphthyl, and R and R ¹ ,
As the heterocyclic group represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ or R ⁷ , for example, a pyridyl group (for example, 2-pyridyl, 3-pyridyl)
Pyridyl, 4-pyridyl, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, chenyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc. Is mentioned.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all R, R ¹ , R ² , R ³ , R ⁴ and R.
^The alkyl group represented by ⁵ , R ⁶ or R ⁷ and a group similar to the groups shown as the substituent of the alkyl group can be substituted.

The substituent represented by R ⁴ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group,
Alkoxycarbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, carboxy group, hydroxy group, hydrogen atom, mercapto Represents a group, an alkylthio group, an arylthio group, an alkenylthio group, a heterocyclic thio group and the like. These groups are R, R ¹ , R ² , R ³ , R ⁴ ,
The alkyl group represented by R ⁵ , R ⁶ or R ⁷ can be substituted with the same groups as the substituents of the alkyl group.

Specific examples of the compounds represented by the general formulas [IV], [V] and [VI] are shown below, but the present invention is not limited thereto.

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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The silver halide emulsion used in the present invention is
Research Disclosure (RD) 308
119 can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine structure 993I-A item Manufacturing method 993I-A item and 994E item Crystal habit Normal crystal 994E item Twin crystal 994E item Epitaxial 994E item Halogen composition uniform 993I- Item B Non-uniform 993I-B item Halogen conversion 994I-C item Halogen substitution 994I-C item Metal-containing 995I-D item Monodisperse 995I-F item Solvent addition 995I-F item Latent image forming position surface 995I-G item Inner surface 995I -G Item Applied Sensitive Material Negative 995I-H Item Positive (including internal fog particles) 995I-H Item used by mixing emulsions 995I-J Item Desalting 995II-A In the present invention, the silver halide emulsion is physically ripened Use those that have been chemically aged and spectrally sensitized. The additives used in such a process are RD17643, 1871
6 and 308119.

The places of description are shown below.

[0170]

[Table 1]

Known photographic additives that can be used in the present invention are also described in the above RD. Below are the relevant locations.

[0172]

[Table 2]

The order of laminating each photosensitive layer is not particularly limited,
Various lamination orders can be adopted according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer in order from the support side. Can be laminated.

The photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivities. For the purpose of improving color reproduction, a fourth or higher color-sensitive photosensitive layer may be provided in addition to the three layers of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer. The layer constitution using the fourth or higher color-sensitive photosensitive layer is described in JP-A-61-34541, JP-A-61-201245, JP-A-61-198236, JP-A-62-160448 and the like. These can be referred to.

In this case, the fourth or more color-sensitive photosensitive layers may be arranged at any laminating position. Also, the fourth
Alternatively, the photosensitive layer having higher color sensitivity may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the above-mentioned photosensitive layers and as the uppermost layer and the lowermost layer.

These non-photosensitive layers are provided in JP-A-61-43.
748, 59-113438, 59-1134
Couplers, DIR compounds, and the like described in JP-A Nos. 40-61, 61-20037, and 61-20038 may be contained, and a color-mixing inhibitor may be contained as usually used. These non-photosensitive layers are RD3
08119, p. 1002, section VII-K, and may be an auxiliary layer such as a filter layer or an intermediate layer.

Examples of the layer structure that can be adopted in the light-sensitive material of the present invention include the normal layer, the reverse layer and the unit structure described in RD308119, page 1002, item VII-K.

When there are two photosensitive layers having the same color sensitivity, these photosensitive layers may be the same, and a high-sensitivity emulsion layer as described in West German Patent 923,045, It may have a two-layer structure of a low-sensitivity emulsion layer. In this case, it is usually preferable that the layers are arranged so that the sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the emulsion layers. Also, JP-A-57-112
No. 751, No. 62-200350, No. 62-2065
As described in JP-A Nos. 41 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, the low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green sensitive layer (GH) / Low sensitivity green sensitive layer (GL) /
Installed in the order of high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH Can be mentioned.

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / from the side farthest from the support.
They can be arranged in the order of RH / GL / RL. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer / G
They may be arranged in the order of L / RL / GH / RH.

Further, as described in JP-B-49-15495, three photosensitive layers having the same color sensitivity with different sensitivities are provided.
Layers can be used. These three layers are arranged as a high-speed emulsion layer in the upper layer, a medium-speed emulsion layer in the middle layer, and a low-speed emulsion layer in the lower layer. Further, as described in JP-A-59-202264, a medium-speed emulsion layer, a high-speed emulsion layer, and a low-speed emulsion layer may be arranged in this order from the side away from the support.

In the case of comprising three layers having different sensitivities, the order of laminating these three layers is arbitrary. For example, the order of laminating is high-sensitivity emulsion layer, low-sensitivity emulsion layer and medium-sensitivity emulsion layer. Order, or low-speed emulsion layer, medium-speed emulsion layer, high-speed emulsion layer and the like. Further, four or more photosensitive layers having the same color sensitivity can be provided, and in this case, the arrangement is arbitrary as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The silver halide emulsion for use in the present invention is, for example, RD17643, pages 22 to 23 (December 1978).
"I. Emulsion preparationan
dtypes), pp. 18716, 648, Grafkides, Physics and Chemistry of Photography, published by Paul Montell (P.
Glafkids; Chemic et Physi
que Photographie, Paul M
Ottel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo.
optic Emulsion Chemist
RY, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al; Makin).
g and Coating Photographi
c Emulsion, FocalPress, 196
It can be prepared using the method described in 4). U.S. Pat. Nos. 3,574,628 and 3,663;
Monodisperse emulsions described in, for example, 5,394 and British Patent 1,413,748 are also preferable.

In the silver halide emulsion, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include the aforementioned RD17643, pp. 23-27, 1871.
6,648-651 and 308119,996 II
Various compounds described in sections IA to 1011, section XX-B can be used.

Various color couplers can be used in the color light-sensitive material.

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, 4,326,024, 4,401,752, 4,248,961 and US Pat. Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 4,314,023.
No. 4,511,649, European Patent 249,473
Those described in No. A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 3,061,432, 3,725,067, 4,310,619 and 4,351 are preferred. , 897, European Patent 73,636, Research Disclosure (hereinafter referred to as RD) 24220, 24230 (June 1984), JP-A-55-118034 and 60-335.
No. 52, No. 60-35730, No. 60-43659
No. 60-185951, No. 61-72238,
U.S. Pat. Nos. 4,500,630 and 4,540,654
No. 4,556,630, International Publication WO88 / 04
No. 795.

Examples of cyan couplers include known phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,228,233, 4,296,200, 2,369,929 and 2,810. 171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173. , West German Patent Publication 3,329,729, European Patent 121,36
Nos. 5A and 249,453A; U.S. Pat.
No. 622, No. 4,333,999, No. 4,775,6
No.16, No.4,451,559, No.4,427,76
No. 7, 4,690,889, 4,254,212
No. 4,296,199, JP-A-61-42658.
Those described in No. 5 and the like are preferable.

For the purpose of correcting unnecessary absorption of the coloring dye, a coupler for correcting unnecessary absorption of the coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,744,181, and US Pat. No. 4,777. It is also preferable to use a coupler having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group described in JP-A No.

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, West German Patent (Publication) 3,234. Those described in No. 533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,080,
No. 211, No. 4,367,282, No. 4,409,3
No. 20, 4,576,910, British Patent 2,10
2, 173, etc.

Couplers which release a photographically useful residue upon coupling are also preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent 2,097,1 can be used.
Nos. 40 and 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,472.
No. 4,338,393, and 4,310,618, multi-equivalent couplers described in JP-A-60-185950.
Compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound described in JP-A-62-24252.
IR redox compound-releasing redox compounds, couplers capable of releasing a dye that becomes bicolored after release described in EP 173,302A, RD11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, US Examples thereof include a ligand releasing coupler described in Japanese Patent No. 4,553,477 and a coupler releasing leuco dye described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are RD17643 mentioned above.
VII-CF and RD308119, 1001-2
Page VII-DF.

The additive used in the present invention is RD3081.
19, XIV, etc. can be added.

The light-sensitive material of the present invention includes, for example, the type and manufacturing number of the photographic light-sensitive material, the manufacturer's name, the emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

In the present invention, the magnetic recording layer is preferably coated on the side of the support opposite to the photographic constituent layer. The undercoat layer, the antistatic layer (conductive layer), It is preferable that the magnetic recording layer and the sliding layer are formed.

As the magnetic substance fine powder used in the magnetic recording layer, metal magnetic substance powder, iron oxide magnetic substance powder, Co-doped iron oxide magnetic substance powder, chromium dioxide magnetic substance powder, barium ferrite magnetic substance powder and the like can be used. . The method for producing these magnetic powders is known and can be produced according to a known method.

The optical density of the magnetic recording layer is preferably small considering the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

The amount of magnetization of the magnetic recording layer per 1 m ² of the light-sensitive material is preferably 3 × 10 ^-2 emu or more. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation with Oe once is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic light-sensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm.
It is preferably from 0.05 to 15 μm, more preferably from 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form the binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Furthermore, it is necessary to adjust the physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add non-magnetic metal oxide particles, especially alumina fine particles.

Examples of the support of the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, polyolefin film and the like. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
No. 93641, No. 2-181749, No. 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

In the present invention, the supports preferably used are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer and the undercoat layer, the same binder as used for the magnetic recording layer can be used.

Further, it is preferable to coat a higher fatty acid ester, a higher fatty acid amide, polyorganosiloxane, liquid paraffin, waxes, etc. on the magnetic recording layer as a sliding layer.

When the light-sensitive material of the present invention is used as a color light-sensitive material for roll-shaped photography, not only can a camera and a cartridge be miniaturized, but also resources can be saved, and a storage space for a developed negative film can be saved. Therefore, the film width is about 20 to 35 mm, preferably 20.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² , preferably 400 to 600 mm ² , it is possible to make a small format without deteriorating the image quality of the final photographic print, and a smaller patrone and a smaller camera than before can be achieved. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 sizes of 1: 1 and half sizes of 1: 1.4, 135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that it is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

In order to obtain a dye image using the color light-sensitive material of the present invention, a commonly known color development process is carried out after exposure. That is, the aforementioned RD17643, pages 28 to 29, R
D18716, pp. 647 and RD308119, 101
It can be developed by the usual method described on page 0, section XIX.

[0215]

【Example】

 Example 1 Preparation of seed crystal emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288 and 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) at the same time while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. Was added over 2 minutes to form nuclei. Subsequently, the liquid temperature was raised to 60 ° C. over 60 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution, and then an aqueous silver nitrate solution (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% potassium iodide) was added over 42 minutes by the simultaneous mixing method while maintaining the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing with water were immediately performed using a usual flocculation method.

The obtained seed crystal emulsion had an average spherical equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of silver halide grains had a maximum side ratio of 1.0.
~ 2.0 hexagonal tabular grains. This emulsion is called seed crystal emulsion-1.

[Solution A1] Ocein gelatin 24.2 g Potassium bromide 10.8 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% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide. While vigorously stirring 5 liters, 7.06
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is called SMC-1.

Preparation of Emulsion Em-1 0.178 mol of seed crystal emulsion-1 and 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) in 10% ethanol solution 0.5
4.5 wt% inert gelatin aqueous solution containing 70 ml
Keep 0 ml at 75 ℃, pAg 8.9, pH 5.0
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 2.1 molar silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was added while keeping the pH at 8.9 and pH at 5.0.

2) Subsequently, 1.028 mol of silver nitrate aqueous solution, 0.032 mol of SMC-1 and potassium bromide aqueous solution were added while keeping pAg at 8.9 and pH at 5.0.

During the formation of particles, each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a grain size (cubic 1 having the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm, an average aspect ratio of 7.2, and a variation coefficient of a projected surface circle equivalent diameter of 24.9%.

When the surface silver iodide content was measured by the method described in this specification, the surface silver iodide content was found to be:
It was 4.5 mol%.

Preparation of Emulsion Em-2 In the preparation of Emulsion Em-1, after the step 2) was completed, 0.0005 per mol of silver halide grain silver grown.
Mole SMC-1 was added and aged for 15 minutes, except
Emulsion Em-2 was prepared in exactly the same manner as Em-1.

The obtained emulsion had a grain size (cubic 1 having the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm, an average aspect ratio of 7.2, and a variation coefficient of a diameter of a circle on the projection plane of 24.5%. The surface silver iodide content was 13.1 mol%.

[0227]

[Table 3]

1) The silver iodide content (mol%) of each phase is shown. X indicates a dislocation line introduction position.

2) Aspect ratio at 50% of the total projected area of silver halide grains in each emulsion.

3) After phase formation with an AgI content of 3 mol%,
Aging was performed by adding 0.004 mol% of SMC-1.

The following sensitizing dyes S-1, S-2, S-3, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to each of the above emulsions Em-1 to Em-2, and the emulsion was prepared according to a conventional method.
Chemical sensitization was performed so that the fog-sensitivity relationship was optimal.

The following stabilizers ST-1 and antifoggants AF-1 were added to each emulsion. The amount of ST-1 added was 1 g per mole of silver halide, and the amount of AF-1 was 15 mg per mole of silver halide.

Magenta coupler M-1 shown below dissolved in ethyl acetate and dioctyl phthalate was added to each of the obtained emulsions.
And further add general photographic additives such as an emulsified dispersion, a spreading agent and a hardening agent to prepare a coating solution, and apply each of the coating solutions on a subbed cellulose triacetate support by a conventional method. , Dried, and 101-102 were produced.

These samples were subjected to wedge exposure through a Toshiba glass filter Y-48 using a 5400K light source according to a conventional method, and developed according to the following processing steps.

Each compound used is shown below.

[0236]

Embedded image

(Treatment Step) Treatment Step Treatment Time Treatment Temperature Replenishment Amount Color Development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 C 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Dry 1 min 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

The sensitivity of each sample was such that the red density was fog +0.
The sample N
o. It was shown as a relative value with the value of 101 as 100.

Further, the sensitivity of the sample after being stored for 14 days in the atmosphere of the temperature of 40 ° C. and the relative humidity of 80% was compared with the sensitivity of the sample after being stored for the same period in the atmosphere of 23 ° C. and the relative humidity of 55%. By doing so, the moisture-resistant storage stability was evaluated.

The results are shown in Table 4.

[0241]

[Table 4]

The samples using the emulsion of the present invention and the sensitizing dye have remarkably improved the reduction in sensitivity at high humidity storage.

Example 2 Preparation of Emulsion Em-3 0.178 mol of seed crystal emulsion-1 and 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) in 10% ethanol solution 0.5
4.5 wt% inert gelatin aqueous solution containing 70 ml
Keep 0 ml at 75 ℃, pAg 8.9, pH 5.0
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 2.1 molar silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was added while keeping the pH at 8.9 and pH at 5.0. 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg was adjusted to 9.8. Thereafter, 0.071 mol of SMC-1 was added and ripening was performed for 2 minutes (introduction of dislocation lines). 3) 0.959 mol of silver nitrate aqueous solution and 0.03 mol of S
MC-1 and an aqueous solution of potassium bromide, pAg of 9.
8. Add while keeping pH at 5.0.

During the formation of particles, each solution was added at an optimum rate so that the formation of new nuclei and Ostwald ripening between particles did not proceed. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a grain size (cubic 1 having the same volume).
The emulsion consisted of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm, an average aspect ratio of 7.0, and a coefficient of variation of a circle equivalent to a projected surface of 27.8%. Observation of this emulsion with an electron microscope revealed that 60% or more of the total projected area of the grains in the emulsion was found to be 5 in both the fringe portion and inside the grains.
More than one dislocation line was observed. The surface silver iodide content is
6.7 mol%.

Preparation of emulsion Em-4 In the preparation of emulsion Em-3, Em-3 was used except that the amount of silver nitrate added in the step 3) was 0.92 mol and the amount of SMC-1 was 0.069 mol. Emulsion Em-
4 was prepared.

The obtained emulsion had a grain size (cubic 1 having the same volume).
The emulsion was composed of tabular grains having a halogen composition shown in Table 1 having a side length of 0.65 μm, an average aspect ratio of 6.7, and a variation coefficient of a projected surface circle equivalent diameter of 28.4%. When this emulsion was observed with an electron microscope, 5 or more dislocation lines were observed both in the fringe portion and inside the grain in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content is
It was 11.9 mol%.

The following sensitizing dyes SD-1, SD-2, SD-3, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to each of the above emulsions Em-3 to Em-4, and fog was applied according to a conventional method. -Chemical sensitization was performed to optimize the sensitivity relationship.

The following stabilizer ST-1 and antifoggant AF-1 were added to each emulsion. The amount of ST-1 added was 1 g per mole of silver halide, and the amount of AF-1 was 15 mg per mole of silver halide.

Magenta coupler M-1 shown below dissolved in ethyl acetate and dioctyl phthalate was added to each of the obtained emulsions.
And further add general photographic additives such as an emulsified dispersion, a spreading agent and a hardening agent to prepare a coating solution, and apply each of the coating solutions on a subbed cellulose triacetate support by a conventional method. , Dried, and 201-202 were produced.

In the same manner as in Example 1, the sensitivity and the sensitivity fluctuation under high humidity storage were evaluated. The sensitivity is the same as sample No. 1 of Example 1.
It is shown as a relative value when the value of 101 is 100. Table 5 shows the results.

[0253]

[Table 5]

Emulsions Em-3 and Em-4 into which dislocation lines have been introduced
Gives high sensitivity to Em-1 and Em-2,
Even in that case, the sample using the emulsion and the sensitizing dye of the present invention remarkably reduces the decrease in sensitivity when stored at high humidity.

Example 3 In preparation of Samples 203 and 204, the amount of sodium thiosulfate used for chemical sensitization was set to 80% and the amount was reduced to 2
Sample 30 was prepared in exactly the same manner except that the chemical sensitization was optimally performed by adding a selenium sensitizer in a molar amount corresponding to 0%.
1, 302 were created.

In the same manner as in Example 1, the sensitivity and the sensitivity fluctuation under high humidity storage were evaluated. The sensitivity is the same as sample No. 1 of Example 1.
It is shown as a relative value when the value of 101 is 100. Table 6 shows the results.

[0257]

[Table 6]

By subjecting to selenium sensitization, an emulsion having higher sensitivity can be obtained. Even in that case, the samples using the emulsion and the sensitizing dye of the present invention show a significantly small decrease in sensitivity when stored at high humidity.

Example 4 Sample No. In the preparation of 301 and 302, Sample 40 in which 60 mg of Exemplified Compound V-3 described in the present specification was added instead of AF-1 antifoggant, was added per mol of silver halide.
Samples 403 and 404 were prepared by adding 60 mg of Exemplified Compound V-3 to the antifoggant AF-1 and 60 mg of the exemplified compound V-3 per mol of silver halide.

In the same manner as in Example 1, the sensitivity, sensitivity fluctuation under high humidity storage and fog fluctuation were evaluated. The sensitivity is the same as sample No. 1 of Example 1. It is shown as a relative value when the value of 101 is 100. Table 7 shows the results.

[0261]

[Table 7]

1) The fog difference between the samples stored at 40 ° C., RH 80% for 14 days and at 23 ° C., RH 55% for 14 days was taken.

The emulsion of the present invention, the sensitizing dye and the general formula (IV)
It has been shown that the sample using the compound represented by the formula not only shows a decrease in sensitivity during storage at high humidity but also has a significantly reduced fogging variation.

Example 5 Samples 501 and 502 were prepared in exactly the same manner as Example 3 except that the sensitizing dyes SD-2 and SD-3 were replaced by equimolar sensitizing dyes SD-4 and SD-5, respectively. Prepared. In the same manner as in Example 1, the sensitivity and sensitivity variation under high humidity storage were evaluated. The sensitivity is the same as sample No. 1 of Example 1. The value of 101 is 1
The relative value is set to 00. Table 8 shows the results.

[0265]

[Table 8]

By performing selenium sensitization in the same manner as in Example 3, an emulsion of higher sensitivity can be obtained, and at the same time, the samples using the emulsion of the present invention and the sensitizing dye showed a decrease in sensitivity at high humidity storage. Is significantly smaller.

Example 6 The support of Example 1 was changed to the following support, and evaluation was performed in the same manner as in Example 1.

<< Preparation of Support >> 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, ethylene glycol 6
0.1 part by weight of calcium acetate hydrate was added to 0 part by weight as a transesterification catalyst, and transesterification reaction was carried out according to a conventional method. The product obtained was treated with antimony trioxide 0.
05 parts by weight and 0.03 parts by weight of phosphoric acid trimethyl ester were added. Then gradually raise the temperature and reduce the pressure, 290 ° C,
Polymerization is performed under the condition of 0.05 mmHg and the intrinsic viscosity is 0.6.
0 of polyethylene-2,6-naphthalate was obtained.

This was vacuum dried at 150 ° C. for 8 hours, then melt-extruded in layers from a T die at 300 ° C., adhered to a cooling drum at 50 ° C. while electrostatically applied, cooled and solidified, and an unstretched sheet Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched by a tenter type transverse stretching machine at 50% of the total transverse stretching ratio at the first stretching zone of 145 ° C, and further at the second stretching zone of 155 ° C at the total transverse stretching ratio of 3. It was stretched so as to be three times. Then 1
Heat treatment at 00 ° C. for 2 seconds,
Heat set at 0 ° C. for 5 seconds, 1 second at 240 ° C.
Heat set for 5 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while performing a 5% relaxation treatment in the lateral direction to obtain a polyethylene naphthalate film having a thickness of 85 μm.

Wrap this around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to form a support.

12 W / m ² / min on both sides of this support
Of the undercoating coating solution B-1
To a dry film thickness of 0.4 μm and then apply 1
A 2 W / m ² / min corona discharge treatment was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment of 12 W / m ² / min, the undercoat coating solution B-3 was applied to give a dry film thickness of 0.
2 μm, and 12 W / m ² / m
An in-corona discharge treatment was performed, and a coating solution B-4 was applied so as to have a dry film thickness of 0.2 μm.

Each layer was dried at 90 ° C. for 10 seconds after coating, and after four layers were coated, heat treatment was performed at 110 ° C. for 2 minutes, followed by cooling treatment at 50 ° C. for 30 seconds.

<Undercoating Coating Liquid B-1> Copolymer latex liquid (30% solid content, 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate). ) 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Undercoating coating solution B-2> Hydroxylation of styrene-maleic anhydride copolymer Aqueous sodium solution (solid content 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size 3 μ) 0.2 g Finish with water 1000 ml <Coating liquid B-3> Butyl Acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxy acrylate 25 % By weight of copolymer latex liquid (solid content 30%) 50 g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (ethylene urea) 1.1 g Finish with water 1000 ml

[0276]

Embedded image

<Coating Liquid B-4> 60 mol% of dimethyl terephthalate as a dicarboxylic acid component, 30 mol% of dimethyl isophthalate, 10 mol% of dimethyl 5-sulfoisophthalate sodium salt, and 50 mol% of ethylene glycol as a glycol component. 50 mol% of diethylene glycol was copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

Aqueous dispersion of tin oxide-antimony oxide composite fine particles (average particle size 0.2 μ) (solid content 40% by weight) 109 g Aqueous dispersion A 67 g Finish with water 1000 ml << Coating of magnetic recording layer >> Undercoat layer U- of the treated support
On the layer coated with the coating liquid, the coating liquid for the magnetic recording layer having the following composition was dried at a dry film thickness of 0.1 using a precision extrusion coater.
The coating was applied so as to have a thickness of 8 μm, and at the same time as drying, the magnetic substance was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

[Composition and Preparation of Magnetic Recording Layer Coating Solution M-1] Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Specific surface area 40 m ² / g, Hc = 750 Oe) 10 parts by weight Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 3 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132, Japan) Polyurethane Co., Ltd. 15 parts by weight Stearic acid 2 parts by weight Cyclohexanone 920 parts by weight Acetone 920 parts by weight After thoroughly mixing and dispersing the above, a polyisocyanate of Coronate-3041 (manufactured by Nippon Polyurethane Co., Ltd., solid) 50% by weight), and then sufficiently stirred and mixed to obtain a magnetic paint M-1.

<< Coating of Lubricating Layer >> A lubricant coating solution (wax solution below) dispersed in a water / methanol mixed solution so as to contain 0.1% of carnauba wax on the magnetic recording layer was prepared. The coating amount was 15 mg / m ² . The raw material after the wax application was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of Wax Liquid) Polyoxyethylene lauryl ether 4 was added to 100 parts by weight of water heated to 90 ° C.
After mixing with 40 parts by weight of carnauba wax separately melted at 90 ° C., the mixture was sufficiently stirred using a high-speed stirring homogenizer to prepare a carnauba wax dispersion (WAX1). .

Next, 995 parts by weight of water, 900 parts by weight of methanol and 10 parts of propylene glycol monomethyl ether.
0 parts by weight, and 5 parts by weight of WAX1 was added thereto.
The mixture was stirred to prepare a wax liquid.

A multilayer color photographic light-sensitive material 601 was prepared by sequentially forming the same layers as in Example 1 from the support side on the side opposite to the side having the magnetic recording layer of the support thus prepared. Further, the silver halide emulsion of Sample 601 was changed as shown in Table 9 below to prepare Samples 602 to 604,
Evaluation was performed in the same manner as in Example 1. Table 9 shows the results.

[0284]

[Table 9]

As is clear from Table 9, good results were obtained in the constitution of the present invention even when this support was used.

[0286]

EFFECT OF THE INVENTION A silver halide emulsion having a high sensitivity and a significant reduction in sensitivity upon storage at high humidity can be obtained.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03C 1/34 G03C 1/34 7/00 510 7/00 510

Claims (7)

[Claims] 1. 50% or more of the total projected area of silver halide grains contained in the emulsion has two or more phases having different silver iodide contents inside the grains, and the maximum iodide content inside the grains is obtained. The tabular grains having a silver iodide content of more than 5 mol% and less than 10 mol% in the silver-containing phase and having a silver iodide content of 10 mol% or more on the surface of the silver halide grains. The silver particles are represented by the following general formula [I], general formula [II] or general formula [III]
A silver halide photographic emulsion characterized by being spectrally sensitized with at least one sensitizing dye represented by Embedded image (In the formula, R ₁₁ represents a sulfoethyl group, and R ₁₂ , R ₂₁ , R
₂₂ , R ₃₁ and R ₃₂ are each a substituted or unsubstituted alkyl group,
A substituent selected from a substituted or unsubstituted alkenyl group and a substituted or unsubstituted alkynyl group, R ₁₃ , R ₂₃ and R
Each of ₃₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z ₁₂ and Z ₃₁ represent an atomic group necessary for forming a substituted or unsubstituted benzoxazole nucleus or naphthoxazole nucleus, and Z ₃₂
Represents an atomic group necessary for forming any of a substituted or unsubstituted benzothiazole nucleus, a naphthothiazole nucleus, a substituted or unsubstituted benzoselenazole nucleus, and a naphthoselenazole nucleus. X ₁ , X ₂ and X ₃ represent charge balancing counterions,
n1, n2 and n3 represent numerical values for controlling the charge of the whole molecule. ) 2. 50% or more of the total projected area of silver halide grains contained in the emulsion has two or more phases having different silver iodide contents inside the grains, and the maximum iodide inside the grains is obtained. Tabular grains having a silver iodide content of more than 5 mol% and less than 10 mol% in the silver-containing phase, and having a silver iodide content of 10 mol% or more on the surface of the silver halide grains; It is a tabular grain containing a dislocation line inside a silver halide grain, and the silver halide grain is at least one of sensitizing dyes represented by the above general formula [I], general formula [II] or general formula [III]. A silver halide photographic emulsion characterized by being spectrally sensitized by. 3. The silver halide photographic emulsion according to claim 1, wherein the silver halide grains are selenium sensitized. 4. A silver halide grain comprising at least one of
4. The silver halide photographic emulsion according to claim 1, wherein the part is a grain formed by using fine silver halide grains. 5. The silver halide photographic emulsion according to claim 4, wherein the fine silver halide grains have a solubility lower than that of the host grains under the grain forming conditions. 6. A silver halide emulsion according to claim 1, which has at least one layer of a light-sensitive silver halide emulsion on a support, and wherein at least one layer of said emulsion is provided. A silver halide color photographic light-sensitive material comprising: 7. A silver halide emulsion according to claim 1, which has at least one layer of a light-sensitive silver halide emulsion on a support, and wherein at least one layer of said emulsion layer is provided. And at least one compound represented by the following general formula [IV] in the emulsion layer or in another hydrophilic colloid layer having a water-permeable relationship with the emulsion layer. Silver halide color photographic light-sensitive material. General formula [IV] Het- (SR) _i (In the formula, Het represents a heterocycle, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
i represents an integer of 0, 1 or 2. However, Het or R has the at least one directly or indirectly groups or salts thereof selected from -SO ₃ H, -COOH or -OH. )