JPH09197611A - Silver halide color photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic material, which is high sensitive with less carnation in photographic performance through aged storage. SOLUTION: A silver halide color photographic material has more than two phases having different contents of silver iodide in particles over an area of higher than 50% of the total projected area, and of these phases, the one having a maximum, content of silver iodide has less than 15mol.% in the content of silver iodide, and contains planer silver halide particles using fine silver halide particles during growth of the particles, and a compound exhibited by the formula: In the formula, R1 and R2 are hydrogen atom, alkyl group the like, respectively, which may form a heterocyclic ring, G is COOR3 , -SO2 R3 or the like, R3 , R4 are hydrogen atom, alkyl group and the like, and n is an integer which is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent storage stability.

[0002]

2. Description of the Related Art In recent years, demands for silver halide color photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials) have become more and more strict. For example, it is natural that they have high sensitivity and excellent image quality, and further, photographic performance during storage with time. At the same time, it is required that fluctuations be kept to a minimum.

A color negative photosensitive material contains various organic and inorganic compounds in the photosensitive material, and these compounds may deteriorate or interact with each other during storage to change the photographic performance of the light-sensitive material. , Often happens. Moreover, it is impossible to elucidate all of their interactions because of the large variety of compounds used. As a result, it is difficult to improve the storage stability, and it is hard to say that it has been sufficiently achieved in practice.

Further, Japanese Patent Application Laid-Open No. 7-92594 and Japanese Patent Application No. 6-
The silver halide emulsion described in No. 312075 is very useful because it has high sensitivity, but at the same time, because of its high sensitivity, it causes photographic performance fluctuations such as fog increase and sensitivity decrease during storage, and its correspondence is required. Was there.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which has high sensitivity and has little fluctuation in photographic performance during storage over time.

[0006]

The above objects of the present invention have been attained by the following constitutions.

(1) 50% or more of the total projected area has two or more phases having different silver iodide contents inside the grain, and among the phases, the phase having the largest silver iodide content Halogen characterized by containing tabular silver halide grains having a silver iodide content of less than 15 mol% and using fine silver halide grains during grain growth, and a compound represented by the following general formula (1): Silver halide color photographic light-sensitive material.

[0008]

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[In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ may form a heterocycle. G is _{-COOR 3, -SO 2 R 3,} -COR 3,
_{-CONR 3 R 4, -SO 2 NR} 3 R 4, represents a -CN,
R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
n represents an integer of 1 or 2. (2) 50% or more of the total projected area has two or more phases having different silver iodide contents inside the grain, and the iodide of the phase having the largest silver iodide content among the phases A halogen having a silver content of less than 15 mol% and containing at least a tabular silver halide grain in which fine silver halide grains are used at the time of forming the outermost layer and a compound represented by the general formula (1). Silver halide color photographic light-sensitive material.

(3) The silver halide color photographic light-sensitive material as described in 1 or 2 above, wherein the fine silver halide grains have a solubility lower than that of the host grains under the conditions for forming silver halide grains.

(4) The silver halide color photographic light-sensitive material as described in 1, 2, or 3, wherein 50% or more of the total projected area is silver halide grains having dislocation lines inside the grains.

(5) The silver halide grains are selenium sensitized, sulfur / selenium sensitized, gold / selenium sensitized or gold / sulfur.
5. The silver halide color photographic light-sensitive material as described in any one of 1 to 4 above, which is a silver halide grain subjected to any one of selenium sensitization.

(6) 50% or more of the total projected area has two or more phases having different silver iodide contents inside the grain, and the silver iodide content is the maximum among the phases excluding the outermost layer. The silver iodide content of the phase is less than 15 mol% and the silver iodide content of at least the outermost layer is 6 mol% or more, and tabular silver halide grains using silver halide fine grains at the time of grain formation are used. A silver halide color photographic light-sensitive material containing the compound represented by the general formula (1).

(7) The silver halide color photographic light-sensitive material as described in 6 above, wherein the silver halide fine grains have a solubility lower than that of the host grains under the silver halide grain forming conditions.

Hereinafter, the present invention will be described in detail. First, the ultraviolet absorbent represented by the general formula (1) used in the present invention will be described.

In the general formula (1), the alkyl group represented by R _{1 to} R ₄ is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a tert group.
-Butyl group, pentyl group, synlopentyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, dodecyl group and the like. These alkyl groups further include a halogen atom (for example, a chlorine atom, a bromine atom,
Fluorine atom), alkoxyl group (eg, methoxy group, ethoxy group, 1,1-dimethylethoxy group, hexyloxy group, dodecyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), aryl Group (for example, phenyl group, naphthyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, 2-ethylhexylcarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, naphthyloxy group) Carbonyl group), alkenyl group (for example, vinyl group,
Allyl group, etc., heterocyclic group (eg, 2-pyridyl group, 3
-Pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group, piperazyl group, pyrimidyl group, pyrazolyl group,
Furyl group etc.), alkynyl group (eg propargyl group etc.), amino group (eg amino group, N, N-dimethylamino group, anilino group etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide It may be substituted with a group (for example, a methylcarphonylamino group, an ethylsulfonylamino group, a butylsulfonylamino group, an octylsulfonylamino group, a phenylsulfonylamino group, etc.).

Examples of the alkenyl group represented by R _{1 to} R ₄ include a vinyl group and an allyl group. These groups can be substituted with an alkyl group represented by R _{1 to} R ₄ and a group similar to the group shown as the substituent of the alkyl group.

Examples of the alkynyl group represented by R _{1 to} R ₄ include propargyl group and the like. These groups can be substituted with an alkyl group represented by R _{1 to} R ₄ and a group similar to the group shown as the substituent of the alkyl group.

The aryl group represented by R _{1 to} R ₄ is
Examples thereof include a phenyl group and a naphthyl group. These groups can be substituted with an alkyl group represented by R _{1 to} R ₄ and a group similar to the group shown as the substituent of the alkyl group.

Examples of the heterocyclic group represented by R _{1 to} R ₄ include a pyridyl group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc.), thiazolyl group, oxazolyl group, imidazolyl group. , Furyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group and the like. These groups can be substituted with an alkyl group represented by R _{1 to} R ₄ and a group similar to the group shown as the substituent of the alkyl group.

Examples of the heterocyclic group which can be formed by R ₁ and R ₂ include a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, a piperazino group and the like. These groups are alkyl groups represented by R _{1 to} R ₄ ,
And a group similar to the group shown as the substituent for the alkyl group.

The general formula (1) used in the present invention is described below.
Specific exemplified compounds of the ultraviolet absorbent represented by are shown below, but the invention is not limited thereto.

[0023]

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[0024]

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In the present invention, the added amount of the ultraviolet absorber represented by the general formula (1) is preferably 0.001 to
3 g / m ² , more preferably 0.005 to 0.6
g / m ² .

The ultraviolet absorber represented by the general formula (1) is
It may be contained in any layer of the photographic constitutional layer, but as is conventionally done, for example, a non-photosensitive layer closest to or adjacent to the support, that is, an antihalation layer or a back layer, and a support. It is preferably contained in the layer farthest from the body side and closest to the light source, or in the non-photosensitive layer adjacent thereto.

Further, when an ultraviolet absorber is contained on the side closer to the light source side than the blue-sensitive layer, the portion of the ultraviolet region of the photosensitive layer of the blue-sensitive layer can be shielded sharply on the long-wave side as much as possible. Since it is preferable to use those, it is effective and preferable that the ultraviolet absorber represented by the general formula (1) is contained on the side closer to the light source side than the blue-sensitive layer.

The ultraviolet absorber represented by the general formula (1) is
It is preferably used in combination with at least one kind of ultraviolet absorber which is liquid at room temperature.

"Liquid at room temperature" means at 25 ° C.
As defined in "Chemical Dictionary (1963) Kyoritsu Shuppan" and the like, those that do not have a fixed shape, are fluid, and have a substantially constant volume are shown. Therefore, the compound having a melting point of 30 ° C. or lower, particularly preferably 15 ° C. or lower, is preferable as long as it has the above properties.

The liquid ultraviolet absorber may be a single compound or a mixture, and as the mixture, those composed of structural isomers can be preferably used (for structural isomers, US Pat. , 587, 346, etc.).

The liquid ultraviolet absorber can have any structure as long as the above conditions are satisfied, but one of the preferable ones is represented by the following general formula [A] from the viewpoint of the light fastness of the ultraviolet absorber itself. 2'-hydroxyphenyl) benzotriazole type compound is mentioned.

[0032]

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In the formula, among the groups represented by R ₃₁ , a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group are preferable, but from the viewpoint of bright and fading, a hydrogen atom, an alkyl group and an alkoxy group are more preferable. Preferably there is.

Of the groups represented by R ₂₉ , R ₃₀ and R ₃₁ , at least one is preferably an alkyl group, and more preferably at least two are alkyl groups in order to be liquid at room temperature. Is preferred.

The alkyl group represented by R ₂₉ , R ₃₀ and R ₃₁ may be any alkyl group, but at least one is preferably a tertiary alkyl group or a secondary alkyl group. Particularly, at least one of the alkyl groups represented by R ₂₉ and R ₃₀ is preferably a tertiary alkyl group or a secondary alkyl group. Further, it is preferable that the total number of carbon atoms in the alkyl portion of the alkyl group is 12 or less. Specific examples of the compound represented by the general formula [A] are shown below.

[0036]

[Chemical 6]

In the present invention, the ultraviolet absorber represented by the general formula (1) may be contained in the photographic constituent layers as long as the ultraviolet absorber is in a liquid state at room temperature, or if necessary. Then, a low boiling point solvent such as ethyl acetate is used to finely disperse it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and this dispersion may be added to the target layer.

Even when these ultraviolet absorbers are solid at room temperature, or even when they are liquid, a high-boiling organic solvent is used, and if necessary, a bottom-boiling solvent is used. Using, finely dispersed in the same manner as above,
Can be added in layers.

An ultraviolet absorber represented by the general formula (1),
The ultraviolet absorber that is liquid at room temperature can be dispersed in the layer at the same time, or separately dispersed in the layer, but is preferably dispersed at the same time.

The silver halide grains will be described in detail below.

In the present invention, the tabular grains mean that the diameter of a circle having two parallel principal planes and having the same projected area as the principal plane and the distance between the principal planes ( That is, it refers to particles having a ratio of particle thickness), that is, an aspect ratio of 2 or more.

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

The diameter of the tabular grains of the present invention is 0.3 to 1
It is 0 μm, preferably 0.5 to 5.0 μm, and 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 can be measured by the methods 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 is such that the variation coefficient of the silver iodide content (the standard deviation of the silver iodide content intergrain distribution divided by the average silver iodide content) is 30% or less. Is preferred and 20% or less is more preferred.

The tabular grains of the present invention have a total projected area of 50
% Or more have at least two phases having different halogen compositions inside the grain, the silver iodide content of the phase having the highest silver iodide content is less than 15 mol%, preferably 5 mol% or more. It is less than 10 mol%. The volume fraction of the particles in the phase is preferably 30 to 90%.
-60% is more preferable.

The silver iodide content of the outermost layer of tabular grains is preferably 6 mol% or more.

The outermost layer referred to in the present invention is a region including the surface area of the particles, but it is not always necessary to completely cover the inner phase. Further, the outermost layer means a region having a thickness of at least 10 atomic layers or more.

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 grain surface" as used in the present invention means either a value measured by the XPS method or a value measured by the ISS method. XPS
When measured by the method, it is preferably 6 to 20 mol%, more preferably 5 to 10 mol%.

The surface silver iodide content by the XPS method of the present invention is determined as follows. The sample was cooled to -115 ° C. or less in an ultrahigh vacuum of 1 × 10 ⁻⁸ torr or less, and MgKα was irradiated as an X-ray for a probe with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d. , I3
Measure for d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the surface is determined from the intensity ratio.

The maximum silver iodide-containing phase referred to in the present invention is
It does not include a high iodine localized region generated by an operation described below for forming a dislocation line.

As the method for producing tabular grains, methods known in the art can be appropriately combined. For example, JP-A 61-6643, 61-146305, and 62.
-157024, 62-18556, 63-9
No. 2942, No. 63-163451, No. 63-220
Known methods such as those of Nos. 238 and 63-311244 can be referred to. For example, a double jet method, a double jet method, a double jet method, a so-called control double jet method for keeping pAg constant in a liquid phase in which silver halide is produced, which is one type of a double jet method, a soluble silver halide having a different composition, respectively, A triple jet method of adding independently can also be used. You can also use the forward mixing method,
Further, a method of forming particles in the presence of excess silver ions (so-called reverse mixing method) can also be used. As the silver halide grains of the present invention, fine silver halide grains are used during grain growth.

A silver halide solvent can be used if necessary. Examples of commonly used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, US Pat.
71,157, 3,790,387, 3,57
No. 4,628 can be referred to. The mixing method is not particularly limited, and a neutral method without ammonia, an ammonia method, an acidic method, or the like can be used, but a pH of 5.5 is preferable from the viewpoint of reducing the fog of silver halide grains. Or less, more preferably 4.5
Prepared below.

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. Alternatively, they may be added as silver iodide fine particles.

In the silver halide emulsion of the present invention, at least the outermost layer having a silver iodide content of 6 mol% or more is formed by using fine silver halide grains. It is preferable that the largest silver iodide-containing layer except the outermost layer is also formed by using fine silver halide grains from the viewpoint of making the halogen composition distribution between grains more uniform and reducing the non-uniformity of the photosensitive quantum efficiency. It is more preferable to grow by using silver halide fine grains throughout the growth. However, the term "grow with silver halide fine particles throughout the grain" in the present invention does not include the seed crystal when the seed crystal is used.

Grain formation using fine silver halide grains
Similarly to the grains disclosed in JP-A-1-183417, JP-A-1-183644, and JP-A-1-183645, grain growth may be carried out using only silver halide grains,
What is necessary is just to supply at least one of the halogen elements by silver halide fine particles. In this case, iodine ions are preferably supplied by silver halide fine grains. As in the claims of JP-A-5-5966,
Two or more kinds of silver halide fine particles are used for grain growth, and at least one of them may be composed of only one kind of halogen element.

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.
Silver iodide is particularly desirable as a silver halide grain having a small solubility product.

In the silver halide grain of the present invention, it is preferable that 50% or more of the total projected area is a tabular silver halide grain having a dislocation line inside the grain. Dislocations of tabular grains are described in F. Hamilton: Photo. S
ci. Eng. , 11 (1967), 57 and T.I. Shi
Ozawa: J.M. Sci. Photo. Sci. Japan
n, 35 (1972), 213, that is, by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to penetrate. Therefore, a clearer observation can be obtained by using a high-pressure electron microscope (200 kV for a thickness of 0.25 μm). . 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 is not particularly required to be at a specific position, but it is preferable that the dislocation is located 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 means the outer periphery of the tabular grain, and more specifically, the perpendicular line drawn from the center of gravity of the tabular grain projection plane viewed from the main plane side to each side of the grain is the perpendicular line. Is outside 50% (side) of the length, preferably outside 70%, and more preferably outside 80%. The dislocation line inside the grain indicates a dislocation line existing in a region other than the above-described fringe portion.

The number of dislocations in the tabular grains is preferably 50% or more of the total projected area of silver halide grains in the emulsion, but 80% or more. Is more preferable. Further, the number of dislocations is more preferably 10 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 dislocation lines is not particularly limited, but a method of adding an aqueous solution of iodide ions such as potassium iodide and a water-soluble silver salt solution by a double jet at a position where dislocations are to be introduced, and silver iodide fine particles are used. It can be carried out by a method of adding, a method of adding only an iodine ion solution, a method of using an iodide ion-releasing agent as described in JP-A-6-11781, or the like. A method of adding an iodine ion aqueous solution and a water-soluble silver salt solution by double jet, a method of adding silver iodide fine particles, and a method of using an iodide ion releasing agent are preferable.
A method using silver iodide fine 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, and 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 used in the 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 groups.

US Pat. Nos. 1,574,944 and 1,6
02,592, 1,623,499, 3,29
7,446, 3,297,447, 3,32
0,069, 3,408,196, 3,40
8,197, 3,442,653, 3,42
0,670, 3,591,385, Japanese Patent Publication No. 52-
34491, 52-34492, 53-295.
No. 57-22090, JP-A-59-180536.
No. 59-185330 and 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
No. 3-24537, No. 3-111838, No. 3-1
No. 16132, No. 3-148648, No. 3-2374
50, 4-16838, 4-25832, 4-25832, 4-32831, 4-960.
No. 59, No. 4-109240, No. 4-140738.
No. 4-147250, 4-149437, 4-184331, 4-190225, 4-1.
91729, 4-195035, 4-2713.
No. 41, No. 4-344636, No. 5-11385,
5-40324, 5-224332, 5-2
No. 24333, No. 6-40324, No. 6-43576.
No. 6, No. 6-75328, No. 6-110149, No. 6
-175258, 6-175259, 6-18
No. 0478, No. 6-208184, No. 6-20818
No. 6, No. 6-265118, No. 6-281642.

The technique concerning selenium sensitization is described in H. E. FIG.
Spencer et al: Journalof Photog
magazine, "Science Science", Volume 31, 158-1
It is also disclosed in scientific literature such as page 69 (1983).

Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (allyl isoselenocyanate, etc.), selenoureas (N, N-dimethylselenourea, N, N, N'-triethyl). Selenourea, N,
N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonyl selenoureas, etc.), selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide,
N, N-dimethylselenobenzamide etc.), selenophosphates (tri-p-triselenophosphate etc.),
Examples thereof include selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.).

Regarding the tellurium sensitizer and the sensitizing method used in the chemical sensitization of the present invention, US Pat.
499, 3,320,069, 3,772,0
No. 31, 3,531,289, 3,655,39
4, British Patent No. 235,211 and 1,121,4.
No. 96, No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 5-303157, No. 6-27573, No. 6-175258, No. 6-175259, No. 6-1.
No. 80478, No. 6-208184, No. 6-2081
No. 86 and the like. Also, Journal of
Chemical Society Chemica
Communication, page 635 (1980).
Year), 645 pages (1979), 1102 pages (19)
1979) and Journal of Chemical
Society Perkin Transacti
on, 1, 191 (1980) and the like.

Examples of useful tellurium sensitizers include telluroureas (N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, etc.) and phosphine telluride. (Tributylphosphine telluride, tricyclohexylphosphine telluride, tri-i-propylphosphine telluride, etc.), telluroamides (telloacetamide, N, N-dimethyl tellurobenzamide, etc.), telluroketones, telluroesters, isotellurocyanate And the like.

The amount of the selenium compound and tellurium compound added is not uniform depending on the compound used, the type of silver halide photographic emulsion, the conditions of chemical ripening, etc., but is usually 1 × 10 ^-8 per mol of silver halide. It is in the range of from 1 × 10 ⁻³ mol, preferably from 5 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol.

These addition methods are, depending on the properties of the selenium compound or tellurium compound used, a method of dissolving in water or an organic solvent such as methanol, ethanol or ethyl acetate, alone or in a mixed solvent, or preliminarily mixed with a gelatin solution. As disclosed in JP-A-4-140739, it is added during 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, and more preferably 6.5 to 9.5. The pH at the time of chemical aging is preferably 4 to 9, more preferably 4.0 to 6.5. The temperature during the chemical aging is preferably 40 to 90 ° C, more preferably 45 to 85 ° C.

For chemical ripening of the silver halide emulsion of the present invention, other chemical sensitizers may be used in combination, and it is particularly preferable to use sulfur sensitizers 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 addition amount of the sulfur sensitizer varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol of silver halide. Is preferred. More preferably, 1 × 10 ⁻⁵ to 1 ×
It is 10 ^-8 mol.

In the present invention, it is also preferable to use a gold sensitizer in combination, and specifically, in addition to chloroauric acid, gold thiosulfate, gold thiocyanate, etc., thioureas, rhodanins and other various compounds. Gold complexes of The amount of the gold sensitizer added varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol of silver halide. Is preferred. More preferably, it is 1 × 10 ⁻⁵ to 1 × 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 is the same. It is preferable to use the sulfur sensitizer in a molar amount or more.

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, it is carried out by ripening or grain growth of a silver halide emulsion or a mixed solution for grain growth under a low pAg of pAg7 or lower or under a high pH condition of pH 7 or higher. You may perform combining these methods.

Further, JP-A-7-219093 and 7-2
As shown in Japanese Patent No. 25438, reduction sensitization may be performed before or after the chemical sensitization step. Further, reduction sensitization may be performed in the presence of an oxidizing agent shown below.

Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salt. Other suitable reducing agents include borane compounds, hydrazine derivatives, formamidine sulfinic acid,
Examples include silane compounds, amines and polyamines, and sulfites. The reducing agent is preferably added in an amount of 10 ^-2 to 10 ^-8 mol per mol of silver halide.

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 during aging is suitably 7 or less, preferably 6 or less, more preferably 1 to 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 of adding the silver salt or 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. Also, the required amount may be added in several divided portions. Prior to the addition of the soluble silver salt and / or the soluble halide 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. Furthermore, the addition may be performed 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, ripening is preferably performed by adding silver nitrate after desalting of the seed particles, and the ripening temperature is preferably 40 ° C or higher and 50 to 80 ° C. The aging time is preferably 30 minutes or more and 50 to 150 minutes.

In the form grown 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, and to increase the pH to 7 or more until the portion corresponding to 50% of the volume of the grown particles grows. More preferably, the particles are grown at least once through an environment of pH 8 or more until a portion corresponding to 40% of the volume of the grown particles grows. Is particularly preferred.

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 Manufacturing method 〃 and 994E Crystal habit Normal crystal 〃 〃 Twin crystal 〃 〃 Epitaxial 〃 Non-uniform halogen composition 993IB Item 〃 〃 Halogen conversion 994I-C 〃 Substitution 〃 Metal 〃 995I-D Monodispersion 995I-F Solvent addition 〃 Latent image forming position Surface 995I-G Inner surface 〃 Application Sensitive material I-H negative 5 99 (Internal fog grains included) 〃 〃 Mixing emulsions 〃 I-J Desalting 〃 II-A In the present invention, the silver halide emulsion used is one that has been physically ripened, chemically ripened and spectrally sensitized. To do. The additives used in such a process are RD17643, 1871
6 and 308119.

The following are the places of description.

[0092]

[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.

[0094]

[Table 2]

Various couplers can be used in the present invention, specific examples of which are described in RD below. The relevant locations are shown below.

[0096]

[Table 3]

The additive used in the present invention is RD3081.
It can be added by the dispersion method described in 19XIV.

The photographic film according to the present invention has the above-mentioned RD.
An auxiliary layer such as a filter layer or an intermediate layer described in the item 308119VII-K can be provided.

The photographic film according to the present invention has the above-mentioned RD3.
Various layers and configurations such as a normal layer, a reverse layer, and a unit configuration described in section 08119VII-K can be used.

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, antistatic layer (conductive layer), It is preferable that the magnetic recording layer and the sliding layer are formed.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic 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, 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.
m is preferred, more preferably 0.05 to 15 μm, and still more preferably 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.

The supports preferably used in the present invention 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 higher fatty acid ester, 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 roll-shaped color light-sensitive material for photographing, not only the downsizing of a camera or a cartridge can be achieved, but also resources can be saved, and a storage space for a developed negative film can be obtained. 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 be 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.

The photographic film according to the present invention has the above-mentioned RD17.
Developing can be carried out by a usual method described in XIX of pages 643, pages 28 to 29, RD18716, page 647 and RD308119.

[0116]

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

Example 1 A multilayer color photographic light-sensitive material sample 1 was prepared by sequentially forming each layer having the following composition from the support side on a triacetyl cellulose film support having an undercoat layer.

Unless otherwise specified, the addition amount indicates the number of grams per 1 m ² . Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First Layer: Antihalation Layer Black Colloidal Silver 0.16 Ultraviolet Absorber (UV-1) 0.20 High Boiling Organic Solvent (Oil-1) 0.12 Gelatin 1.53 Second Layer: Intermediate Layer Color Antifouling agent (SC-1) 0.06 High boiling point organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: low sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, iodide) Silver iodide content 8.0 mol%) 0.43 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.15 Sensitizing dye (SD-1) 2. 8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 sensitizing dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.025 High Point solvent (Oil-1) 0.49 Gelatin 1.14.

Fourth Layer: Medium Sensitive Red Sensitive Layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content rate 8.0 mol%) 0.89 Silver iodobromide emulsion (average grain size of 38 μm, silver iodide content 8.0 mol%) 0.22 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing dye ( SD-3) 1.6 × 10 ^-4 Cyan coupler (C-1) 0.45 Colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 High boiling solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) ) 1.3 × 10 ^-4 sensitizing dye (SD-2) 1.3 × 10 -4 sensitizing dye (SD-3) 1.6 × 10 -4 cyan coupler (C-2) 0.20 Ca Dossian coupler (CC-1) 0.034 DIR compound (D-3) 0.001 High boiling point solvent (Oil-1) 0.57 Gelatin 1.10 6th layer: intermediate layer Color stain inhibitor (SC- 1) 0.075 high boiling point organic solvent (Oil-2) 0.095 gelatin 1.00 7th layer: intermediate | middle layer gelatin 0.45.

Eighth Layer: Low Sensitivity Green Sensitive Layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.64 Silver iodobromide emulsion (average grain size of 27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-4) 7.4 × 10 ⁻⁴ Sensitizing dye (SD-5) 6.6 × 10 ⁻⁴ Magenta coupler (M -1) 0.19 Magenta coupler (M-2) 0.49 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.81 Gelatin 1.89 9th layer: Medium sensitivity green sensitivity Layer Silver iodobromide emulsion A (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.76 Sensitizing dye (SD-6) 1.5 × 10 ⁻⁴ Sensitizing dye (SD- 7) 1.6 × 10 ⁻⁴ Sensitizing dye (SD-8) 1.5 × 10 ⁻⁴ Magenta coupler (M-1) 0.043 Magenta coupler (M-2) 0 .10 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.37 Gelatin 0.76.

Layer 10: High-sensitivity green-sensitive layer Silver iodobromide emulsion B (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.46 Sensitizing dye (SD-6) 93 × 10 ^-4 sensitizing dye (SD-7) 0.97 × 10 ^-4 sensitizing dye (SD-8) 0.93 × 10 ^-4 Magenta coupler (M-1) 0.08 Magenta coupler (M- 3) 0.133 Colored magenta coupler (CM-2) 0.014 High boiling point solvent (Oil-1) 0.15 High boiling point solvent (Oil-2) 0.42 Gelatin 1.08 11th layer: Yellow filter layer Yellow Colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 Formalin scavenger (HS-1) 0.14 High boiling point solvent (Oil-2) 0.21 Gelatin 0.73 12th layer: Intermediate layer Formalin scavenger (HS-1) 0.18 gelatin 0. 60.

Thirteenth Layer: Low Sensitivity Blue Sensitive Layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content rate 8.0 mol%) 0.073 Silver iodobromide emulsion (average grain size 0. 38 μm, silver iodide content 3.0 mol%) 0.16 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 sensitizing dye (SD-9 ) 2.1 × 10 ⁻⁴ Sensitizing dye (SD-10) 2.8 × 10 ⁻⁴ Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling point solvent (Oil-2) ) 0.37 Gelatin 1.51 14th layer: high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 0.95 Sensitizing dye (SD- 9) 7.3 × 10 ^-4 sensitizing dye (SD-10) 2.8 × 10 -4 yellow coupler (Y-1) 0.16 high boiling solvent (Oil-2) 0.0 3 Gelatin 0.80 Fifteenth layer: First protective layer Silver iodobromide emulsion (average grain size: 0.05 μm, silver iodide content: 3.0 mol%) 0.30 Ultraviolet absorber (UV-1) 094 UV absorber (UV-2) 0.10 Formalin scavenger (HS-1) 0.38 High boiling point solvent (Oil-1) 0.10 Gelatin 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent PM -1 (average particle size 2 m) 0.15 Polymethylmethacrylate (average particle size 3 m) 0.04 Sliding agent (WAX-1) 0.02 Gelatin 0.55.

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizer ST-1, dyes AI-1, AI-2,
Antifoggant AF-1, weight average molecular weight: 10,000
And 2 kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 100,000, a hardener H-1, H-2 and a preservative DI-1 were added. The amount of DI-1 added is 9.4.
mg / m ² .

The structures of the compounds used in the above samples are shown below.

[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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The silver halide emulsion of Sample 1 was prepared according to the method disclosed in JP-A-7-92594.
The silver iodobromide emulsions A and B used in the ninth and tenth layers were used.
Of silver iodide from the inside of the grain is 6/30/7 /
A silver halide emulsion consisting of twinned grains having a silver halide composition of 0 mol% and an average aspect ratio of 2.0.

The silver halide emulsion according to the present invention was prepared as follows.

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) by a simultaneous mixing method while keeping the silver potential saturated silver-silver chloride electrode as a reference electrode and a silver ion selective electrode) at 0 mV. It took 2 minutes to add and perform nucleation. 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 sphere-converted 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.
The emulsion consisted of hexagonal tabular grains of .about.2.0.
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
0.5 m of 10% ethanol solution of (CH ₂ CH ₂ O) _n H (m + n = 9.77)
4.5 wt% inert gelatin aqueous solution 700 containing 1
After keeping ml at 75 ° C., adjusting pAg to 8.9 and pH to 5.0, particles were formed by the following procedure by the simultaneous mixing method with vigorous stirring.

1) 1.68 mol of silver nitrate aqueous solution and 0.1
56 mol of SMC-1 and an aqueous potassium bromide solution were added to p
Ag was added at 8.9 and pH was maintained 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. After completion of the addition, 0.05 mol of SMC-1 was added per 1 mol of the grown silver halide, and ripened for 15 minutes.

During the formation of particles, each solution was added at an optimum rate so as to prevent the formation of new nuclei and the aging of Ostwald 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 silver iodobromide emulsion was composed of tabular grains having a halogen composition of 2 / 8.5 / 3 mol% from the inside of the grain having a side length of 0.62 μm and an average aspect ratio of 7.2. .

When the surface silver iodide content was measured by the method described in this specification, the surface silver iodide content was 1
3.1 mol%.

Preparation of Emulsion Em-2 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8
0.5 m of 10% ethanol solution of (CH ₂ CH ₂ O) _n H (m + n = 9.77)
4.5 wt% inert gelatin aqueous solution 700 containing 1
After keeping ml at 75 ° C., adjusting pAg to 8.9 and pH to 5.0, particles were formed by the following procedure by the simultaneous mixing method with vigorous stirring.

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) Then, the solution was cooled to 60 ° C. and pAg
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes. (Introduction of dislocation line) 3) 0.92 mol of silver nitrate aqueous solution and 0.068 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 grain formation, each solution was added at an optimal rate so that the formation of new nuclei and Ostwald ripening between grains 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).
A silver iodide having a halogen composition of 2 / 8.5 / x / 3 mol% (x is a dislocation line introduction position) from the inside of the grain having a side length of 0.65 μm and an average aspect ratio of 6.7; This was a silver iodobromide emulsion composed of flake-like grains. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%
Met.

To the obtained Em-1 and Em-2, the same sensitizing dyes as in the emulsions of the ninth and tenth layers, silver iodobromide emulsion A and silver iodobromide emulsion B, respectively, were added in the same amounts. After that, triphosphine selenide, Na thiosulfate, chloroauric acid and potassium thiocyanate were added, and chemical sensitization was performed according to a conventional method so that the fog-sensitivity relationship was optimized.

Multilayer samples 2 to 17 were prepared with the same constitution except that the silver halide emulsions of the ninth and tenth layers and the ultraviolet absorber of the fifteenth layer of sample 1 were replaced as shown in Table 4. .

Each sample was processed into a usual 135 size, packed in a cartridge, and sealed in a plastic container in an atmosphere of 20 ° C. and 55% relative humidity.

The following evaluations were performed on the above samples.

<< Sensitivity Immediately After Application, Fog >> Each sample was exposed to a white neutral wedge and was subjected to the development processing described below. After drying, the red light transmission density was measured by a density measuring instrument manufactured by X-rite, and sensitometry was obtained. Fog is the minimum density (Dmin) of sensitometry, and Dmin + 0.3
The sensitivity was calculated from the reciprocal of the exposure dose giving the density of.

<< Sensitivity with Time, Fog >> Deterioration with time is caused by leaving each sample in an atmosphere of 40 ° C. and 60% relative humidity for 5 days, and then exposing and developing it in the same manner as the sample immediately after coating to make sensitivity. And fogging was sought. The results are shown as relative values with the sensitivity and fog of Sample 1 immediately after coating as 100, respectively.

The results are summarized in Table 4.

<< Color Development Processing >> (Processing Step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml Fixed 1 minute 30 Second 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Dry 60 seconds 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

<Preparation of Processing Agent> (Color developer composition) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added 1 Finish with 0.01 potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

(Color development replenisher solution composition) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make 1.0 l, potassium hydroxide or 20
The pH is adjusted to 10.18 with% sulfuric acid.

(Bleaching liquid composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1.0 l and aqueous ammonia was added. Alternatively, the pH is adjusted to 4.4 using glacial acetic acid.

(Bleach Replenisher Composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Water was added to make 1.0 l, and ammonia was added. Adjust to pH 4.4 with water or glacial acetic acid.

(Fixer Formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water is added to adjust the volume to 1.0 l, and the pH is adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Fixing Replenisher Solution Formulation) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Water is added to make 1.0 l, and the pH is adjusted to 6.5 with aqueous ammonia or glacial acetic acid.

(Stabilizer and stable replenisher formulation) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Water is added to finish to 1.0 l, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

[0167]

[Table 4]

From Table 4, it can be seen that the samples of the present invention have high sensitivity and excellent storage stability over time.

Example 2 (Preparation of support) To 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol,
0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was performed according to a conventional method. To the obtained product, 0.05 part by weight of antimony trioxide and 0.03 part by weight of trimethyl phosphate ester were added. Then gradually raise the temperature and reduce the pressure to 290 ° C / 0.05.
Polymerization was carried out under the condition of mmHg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

After vacuum-drying this at 150 ° C. for 8 hours, it was melt extruded at 300 ° C. in layers from a T-die to 50 ° C.
While being electrostatically applied onto the cooling drum of (1), the mixture was cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The uniaxially stretched film thus obtained was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone of 155 ° C. in a total transverse stretching ratio of 3 It was stretched so as to have a stretch ratio of 3 times. Then 10
Heat treatment at 0 ℃ for 2 seconds, then the first heat setting zone 200 ℃
Was heat-set for 5 seconds, and second heat-setting zone was set at 240 ° C. for 15 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
Undercoat coating solution B-
1 to a dry film thickness of 0.4 μm, and then apply 1
A corona discharge treatment of ² W / m ² / min was performed, and the undercoat coating solution B-2 was applied to a dry film thickness of 0.06 μm.

On the other surface of the support which had been subjected to corona discharge treatment, an undercoating coating solution B-3 was applied to give a dry film thickness of 0.2 μm, and a corona discharge of 12 W / m ² / min was applied thereon. The conductive layer coating solution B-4 is dried to a film thickness of 0.2 μm.
Was applied so that

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> butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate copolymer (30: 20: 25: 25 weight ratio) latex liquid (solid content 30%) 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finished with water 1 liter <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 μm) 0.2 g Finish with water 1 liter <Undercoating coating liquid B-3> butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate copolymer (30: 20: 25: 25 weight ratio Latex solution (solid content 30%) 50 g Compound (UL-1) 0.3g hexamethylene-1,6-bis (ethyleneurea) 1 liter finished with 0.3g water

[0177]

Embedded image

<Conductive Layer Coating Liquid B-4> Aqueous dispersion of tin chloride-antimony oxide composite fine particles (average particle size 0.2 μm) (solid content 40%) 109 g Water dispersion liquid * 67 g Finished with water 1 liter * Dimethyl terephthalate (60 mol%), dimethyl isophthalate (30 mol%) and 5-sulfoisophthalic acid dimethyl sodium salt (10 mol%) as dicarboxylic acid components, and ethylene glycol (50 mol%) and diethylene glycol (50 mol%) as glycol components are usually used. Was copolymerized by the method. This copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% dispersion liquid.

(Coating of magnetic recording layer) A magnetic recording layer coating solution M-1 having the following composition was formed on the conductive layer of the above-mentioned undercoated support.
Using a precision extrusion coater, dry film thickness of 0.
The coating was carried out so as to have a thickness of 8 μm, and the magnetic substance was oriented in the coating direction in the orientation magnetic field before the coating film was dried, so as to achieve high output during magnetic recording and reproduction.

<Magnetic Recording Layer Coating Liquid M-1> Cobalt-containing γ-iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, non-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) 2 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132: manufactured by Nippon Polyurethane Co.) 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, disperse with a sand mill to obtain polyisotoanato (Coronate 3041: Nippon Polyurethane Co., solid content 50%) 24 parts by weight. After adding
The magnetic recording layer coating liquid was obtained by sufficiently stirring and mixing.

(Coating of Lubrication Layer) On the magnetic recording layer,
A lubricating layer coating solution (wax solution * below) was prepared by dispersing a carnauba wax in a water / methanol mixed solution so that the coating amount of the wax solution was 30 mg / m ² . The wax raw fabric was dried by passing it through a heat treatment zone of 100 ° C. for 5 minutes, and then left standing in an oven of 40 ° C. for 5 days to sufficiently carry out crosslinking reaction of isocyanate.

* 100 parts by weight of water at 90 ° C. was mixed with 4 parts by weight of polyoxyethylene lauryl ether, and another 90 parts
40 parts by weight of carnauba wax that had been melted at 0 ° C was added, and the mixture was thoroughly stirred using a high-speed stirring homogenizer,
A carnauba wax dispersion (WAX-I) was obtained. next,
Water (995 parts by weight), methanol (900 parts by weight) and propylene glycol monomethyl ether (100 parts by weight) were mixed, and 5 parts by weight of WAX-I was added and stirred to obtain a lubricating layer coating liquid.

On the surface of the support thus prepared opposite to the surface having the magnetic recording layer, the same layers as in Example 1 were coated to prepare a multilayer color light-sensitive material sample, and the same evaluation was carried out. The results are shown in Table 5.

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[Table 5]

It can be seen that the combination of the present invention gives a color light-sensitive material excellent in storage stability over time.

[0186]

According to the present invention, a color light-sensitive material having high sensitivity and excellent storage stability over time can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03C 1/09 G03C 1/09 7/00 510 7/00 510

Claims (7)

[Claims] 1. 50% or more of the total projected area has two or more phases having different silver iodide contents inside the grain, and the iodide of the phases having the largest silver iodide content among the phases. Halogenation characterized by containing tabular silver halide grains having a silver halide content of less than 15 mol% and using silver halide fine grains during grain growth, and a compound represented by the following general formula (1): Silver color photographic light-sensitive material. Embedded image [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ may form a heterocycle. G
-COOR _3, -SO ₂ R ₃ is, -COR _3, -CONR _{3
R 4, -SO 2 NR 3 R} 4, represents a -CN, represent R _3, R ₄ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n is 1 or 2
Represents an integer. ] 2. 50% or more of the total projected area has two or more phases having different silver iodide contents inside the grain, and the iodide of the phases having the largest silver iodide content among the phases. A silver halide content of less than 15 mol% and at least the tabular silver halide grains using fine silver halide grains at the time of forming the outermost layer, and a compound represented by the general formula (1). Silver halide color photographic light-sensitive material. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide fine particles have a solubility lower than that of the host particles under the conditions for forming silver halide particles. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein 50% or more of the total projected area is a silver halide grain having a dislocation line inside the grain. 5. The silver halide grain is a silver halide grain subjected to any one of selenium sensitization, sulfur / selenium sensitization, gold / selenium sensitization, and gold / sulfur / selenium sensitization. A silver halide color photographic light-sensitive material according to any one of claims 1 to 4, which is characterized by the above-mentioned. 6. 50% or more of the total projected area has two or more phases having different silver iodide contents inside the grain, and the silver iodide content is maximum in the phases excluding the outermost layer. Tabular silver halide grains having a silver iodide content of a certain phase of less than 15 mol% and a silver iodide content of at least the outermost layer of 6 mol% or more, and using silver halide fine grains during grain formation, A silver halide color photographic light-sensitive material comprising a compound represented by the above general formula (1). 7. The silver halide color photographic light-sensitive material according to claim 6, wherein the silver halide fine grains have a solubility lower than that of the host grains under the conditions for forming silver halide grains.