JPS62105142A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To remarkably improve a granularity and sharpness by specifying the iodine content and occupying ratio of silver in the 1st coating layer and incorporating a non-diffusive coupler which forms an adequately blurring diffusive dye by reacting with the resultant product of oxidation of a color developing agent into a silver halide emulsion layer. CONSTITUTION:The iodine content of the 1st coating layer is made larger by >=10mol% than the iodine content of the internal nuclei and the silver is incorporated into the 1st coating layer so as to occupy 0.01-90mol% of the entire silver halide particle in a process for producing the silver halide particles having 3-layered structure. The non-diffusive coupler which forms the adequately blurring diffusive dye by reacting with the oxidant of the color developing agent includes the compd. expressed by formula [A]. In formula, Cp denotes a diffusible coupler component which generates adequate blurring of a color image and improves the granularity, X is a component contg. a ballast group of 8-32C which is the group to couple with the coupling position of the coupler component and to eliminate by the reaction with the oxidant of the color developing agent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and in particular, a silver halide photographic material having improved graininess and sharpness (or sharpness) at the same time. It relates to color photographic materials (hereinafter referred to as color photographic materials or sensitive materials).

In general, multi-layer color photographic materials must have high sensitivity, the outline of the image must be clear, and the images must be rendered without blurring, that is, the sharpness must be good, and particles must not be rare. required. In particular, color negative photographic materials used as intermediate media for obtaining enlarged print images are required to have good sharpness and no noticeable graininess in accordance with the enlargement magnification. In addition, as cameras have become smaller in recent years, the size of color photographic images has become smaller, and the demand for them has become increasingly strong.

Conventionally, various methods have been known to improve the graininess and sharpness of color photographic materials.One technique for improving graininess is to add a coupler with a fast coupling reaction to the emulsion layer, which is the more sensitive of the two layers with the same color sensitivity. The method described in U.S. Pat.

U.S. Pat. No. 3,1143, in which at least one of the green-sensitive layer and the red-sensitive layer is composed of three partial layers, and the top layer and the middle layer have a maximum color density of 0.60. Although the photosensitive material described in No. 169 is known, it is still insufficient to meet recent demands for improving graininess and sharpness at the same time.

As a technique for improving sharpness, Japanese Patent Application Laid-Open No. 51-1170
No. 32 and No. 52-115219 disclose a technique for reducing the amount of silver halide and improving sharpness by using a new two-equivalent coupler. In addition, the special public service 1977-
No. 26134 discloses a technique in which a silver halide emulsion having an average grain size of 0.3 to 3 m is mixed with 0.2 ml or less of silver halide, which has substantially no sensitivity. U.S. Pat. No. 3,658.5:16 discloses that by placing a part of the blue-sensitive emulsion layer under the green-sensitive or red-sensitive emulsion layer, the influence of light scattering on the green-sensitive layer or the red-sensitive layer is reduced. A technique to improve sharpness is described. Similarly, a technique for forming part of the green-sensitive layer as the uppermost layer is described in Japanese Patent Publication No. 37018/1983. On the other hand, for 8m/+ sensitive materials, acidic dyes are used as anti-irradiation dyes to improve sharpness, and the technology for using them is disclosed in Japanese Patent Application Laid-open Nos. 53-139522 and 51-7.
It is described in No. 7327, etc. In addition, techniques for improving sharpness by providing an antihalation layer are known, and are disclosed in Japanese Patent Application Laid-open Nos. 50-46133 and 52-11712.
No. 2, No. 53-5624. These techniques improve M by reducing the lateral diffusion of light.
TF (Modulation Transfer Fa
Modulation Transfer function This is a technology that improves the high frequency region of the curve, and although the sharpness can be significantly improved individually, it can be desensitized by using an anti-irradiation dye or by providing an anti-halation layer. It has the disadvantage of arising.

It is known that sharpness can also be improved by utilizing the contiguous effects of certain diffusive substances released during development. This effect is due to a local concentration change (concentration gradient) in the color photographic light-sensitive material of the diffusion suppressing substance released during development. There are known methods such as a method in which stirring is performed weakly, and a method in which a light-sensitive material contains a compound that reacts with the oxide of a developing agent to release a diffusive development-inhibiting substance.

Among these, compounds that react with the oxide of a developing agent to release a diffusible development inhibitor include 1, for example, U.S. Pat.
48,052 and 3,227,554 (hereinafter referred to as D
IR coupler) or US patent], 6:12.
Compounds (hereinafter referred to as DIR substances) that release development inhibitors and do not form dyes by coupling with oxidized forms of color developing agents, such as those described in No. 145, are known (hereinafter referred to as DIR couplers and DIR substances). Together with D
Collectively called IR compounds. ).

These adjacency effects of diffusible development-inhibiting substances released during development are described in many patent specifications and publications in addition to the above-mentioned patents.

Also, JP-A-52-82424, JP-A No. 52-11762
No. 7 discloses a new IR coupler and states that it has improved color reproducibility and sharpness. However, these publications do not describe a technique for maximizing the sharpness improvement effect of the DIR coupler. Although it is known that the adjacent effect of the diffusive development inhibitor released during development improves sharpness, it is still not at a satisfactory level, and further improvements in sharpness are desired. .

Therefore, an object of the present invention is to provide a silver halide color light-sensitive material which has greatly improved graininess and sharpness.

[Means for solving the problem] The color photosensitive material according to the present invention that achieves the above object has at least one silver halide emulsion layer on a support,
and an inner core in which 10% (by weight) or more of the photosensitive silver halide grains present in the silver halide emulsion layer is made of silver bromide or silver iodobromide, and silver iodide or iodobromide is present on the outside of the inner core. A projected area consisting of a first coating layer made of silver oxide and a second coating layer made of silver bromide or silver iodobromide having a different halide composition from that of the first coating layer on the outside of the first coating layer. In silver halide grains having a diameter-to-thickness ratio of less than 5, (1) the iodine content of the first coating layer is 10 mol% or more higher than the iodine content of the inner core, and (2) with respect to the entire grain. The silver halide emulsion layer in which the proportion of silver in the first coating layer is 0.01 to 90 mol % is a non-containing material that reacts with the oxidation product of the color developing agent to form a diffusible dye that causes appropriate dye bleeding. It is characterized by containing a diffusible coupler.

The present invention will be explained in detail below.

The size of the silver halide grains of the present invention is expressed by the projected area diameter, where the projected area diameter refers to the diameter of a circle with an area corresponding to the projected area of the grain.

The size of the silver halide grains of the present invention is 0.1 to 5.
．． 0 gm is preferable, and 0.2 to 3.0 Bm is more preferable.

Further, the ratio of the projected area to the thickness is less than 5, and the thickness here refers to the shortest length of the diameter passing through the center of gravity of the particle.

When the inner core of the present invention is composed of silver iodobromide, it is preferably a homogeneous solid solution phase. Here, homogeneous means that the silver iodide content is 95 mol % or within ±40% of the average silver iodide content.

Regarding the halogen composition of the internal core, the average content of iodine is preferably 10 mol% or less, more preferably 0 to 10% by mole.
It is 5 mol%, particularly preferably 0 to 3 mol%.

The proportion of silver in the inner core relative to the silver in the entire particle is preferably 0.01 to 20 mol%, more preferably 0.11 to 20 mol%.
~15 mol%.

The silver iodide content of the first coating layer is 10 mol% or more higher than the silver iodide content of the inner core, preferably 15 mol% or more, particularly preferably 20 mol% or more.

Further, the silver iodide content of the first coating layer is 10 mol% to
100 mol%, preferably 15 mol% to 100 mol%
It is mol%, more preferably 20 mol% to 100 mol%.

The proportion of silver in the first coating layer relative to the total silver in the particles is preferably 0.01 to 90 mol%, more preferably 0.01 to 90 mol%.
．． 0.01 to 80 mol%, particularly preferably 0.02 to 70 mol%.

When the second coating layer consists of silver iodobromide, it does not necessarily have to be homogeneous, but it is more preferably a homogeneous silver iodobromide.

Furthermore, it is necessary for the second WIN to sufficiently cover the first coating layer, and for this reason, the average thickness of the second coating layer is preferably 0.021 Lm or more, more preferably 0.021 Lm or more.
04 Hirom or more.

The silver iodide content of the second coating layer is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, particularly preferably 0 to 10 mol%.
It is 3 mol%.

Further, the silver iodide content of the second coating layer is preferably lower than that of the first coating layer.

The proportion of silver in the second coating layer relative to the total silver of the particles is preferably 1 to 50 mol%.

Although the size distribution of the silver halide grains of the present invention is arbitrary, monodispersity is more preferable. Here, monodisperse means a dispersion system in which 95% of the particles have a size within ±60%, preferably within ±40% of the number average particle diameter. Here, the number average particle diameter is the number average diameter of the projected area diameter of particles.

The proportion of silver halide grains in the emulsion layer containing the silver halide grains of the present invention may be arbitrarily selected, but is preferably 40% or more in terms of silver amount based on all silver halide grains. , particularly preferably 90% or more.

The method for producing the silver halide emulsion of the present invention will be described next.

That is, generally, after forming a nucleus (inner nucleus) consisting of silver bromide or silver iodobromide (iodine content of 10 mol% or less), iodobromide is added onto the nucleus by a halogen substitution method or a coating method. A first coating layer made of silver or silver iodide is formed, and a second coating layer made of silver iodobromide or silver bromide having a different halogen composition from that of the first coating layer is provided on the first coating layer. In the method for producing 3N structure silver halide grains, the iodine content of the first coating layer is 10 mol % or more higher than the inner core, and the amount of silver in the first coating layer is 0% of the entire silver halide grain.
．． 01 to gO mol%.

The details are explained below.

First, the inner core of the silver halide grain of the present invention contains P, Gl
Chimie et Physigu by afkides
e Photography (Paul M.
onte1, 1967), G, F, Duffin
Author Photographic Emulsion Ch
emistry (published by The Focal Press,
(1966), V. [, Zelikman et al.
Making and CoatingPho by al
tographic Emulsion (The F
ocal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which llAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystalline shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

When adjusting the internal core of silver halide grains, it is preferable to have a uniform halogen composition, and when the internal nucleus is silver iodobromide, it is preferable to use a double jet method or a controlled double jet method. ,
When the inner core is silver bromide, the one-sided mixing method is preferred.

The pAg when adjusting the internal core varies depending on the reaction temperature and the type of silver halide solvent, and is preferably 7 to 11. Further, since the grain formation time can be shortened by using a silver halide solvent, it is preferable to use a generally well-known silver halide solvent such as ammonia or thioether.

Even though the shape of the internal core is plate-like, monospherical, and twin-crystalline,
Furthermore, an octahedron, a cube, a tetrahedron, or a mixed system can also be used.

Further, the inner core may be polydisperse or monodisperse, but monodisperse is more preferable. here.

"Monodisperse" has the same meaning as described above.

Also, to make the particle size uniform, British patent 1.53
No. 5,015, Special Publication No. 48-36890, No. 52-16
364, etc., there is a method of changing the addition rate of silver nitrate or alkali halide aqueous solution depending on the grain growth rate, and as described in U.S. Pat. It is preferable to use a method of changing the concentration of an aqueous solution as described above to grow the silver halide grains quickly within a range that does not exceed the critical superease degree. Therefore, it is preferably used when introducing the first and second coating layers described later.

In the process of forming the inner core of silver halide grains or physically ripening, cadmium salt, zinc salt, lead salt, talicum salt,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting.

The first WI layer of the silver halide grains of the present invention can be provided by a conventional halogen substitution method, a silver halide coating method, etc. after subjecting the formed internal cores to a desalting step, if necessary.

The halogen substitution method can be carried out, for example, by adding an aqueous solution consisting mainly of an iodo compound (preferably potassium iodo), preferably at a concentration of 10% or less, after the internal core has been formed. At this time, 0.01 to 0.01 to the number of moles of silver in the entire finished particle
90 mol % of iodo compound is added. At this time, 9Ag is preferably 5 to 12. Specifically, it can be carried out by the method described in U.S. Pat. No. 2,592,250, U.S. Pat. can. At this time, in order to reduce the difference in iodine distribution between particles in the first coating layer, it is desirable to add the iodine compound aqueous solution over 10 minutes or more at a concentration of 10 -2 mol % or less.

Further, as a method for newly coating the inner core with silver halide, it can be carried out, for example, by simultaneously adding a halide aqueous solution and a silver nitrate aqueous solution, that is, by a simultaneous mixing method or a controlled double jet method. For details, see JP-A No. 53-22408 and JP-A No. 43-1316.
No. 2, J.

This can be carried out by the method described in Phto, Sci, 24, 198 (1976).

The pAg when forming the first coating layer varies depending on the reaction rate and the type and amount of the silver halide solvent, and is preferably used in the same manner as described above.

As a method for forming the first m-layer, a simultaneous mixing method or a controlled double jet method is more preferable.

The second coating layer of the silver halide grains of the present invention further includes a silver halide having a halogen composition different from that of the first coating layer on the outside of the inner core having the first coating layer on the surface. It can be provided by a coating method using a mixing method or a controlled double jet method.

Regarding these methods, the method of providing the first coating layer described above is similarly used.

When introducing the second rlI layer, since the halogen composition of the second coating layer is different from that of the first coating layer, the second coating layer is difficult to precipitate on the surface of the first coating layer. Therefore, it is necessary to consider changes in the critical supersaturation degree. Further, it is preferable to increase the number of moles added per unit time as the total surface area of the particles increases.

When the second coating layer is silver bromide, it is also possible to use a method (one-sided mixing method) in which an aqueous silver nitrate solution is added in the presence of the inner core that has bromide and the first coating layer in advance.

Is it preferable that the halogen composition of the second Wt layer be uniform? For this purpose, if the second coating layer is made of silver iodobromide, it is necessary to form it by a simultaneous mixing method or a controlled double jet method. is preferred. Further, when the second coating layer is silver bromide, it is preferable to use a one-sided mixing method.

Regarding the iodine content of the first coating layer of the silver halide grains of the present invention, for example, J, 1. Goldstein (
Goldstein), D. B., Williams (Wi.
llials) r X-ray analysis in TEM/ATEM" Scanning Electron-Microscope (1977), 1s (FIT') 4t f
・Institute), p. 651 (March 1977)
It can also be obtained by the method described in

In preparing the silver halide grains of the present invention, soluble salts are removed from the emulsion after precipitation of the second coating layer or physical ripening or, if necessary, from the emulsion after internal nucleation or after formation of the first coating layer. For this purpose, the Nodel water washing method, which involves gelatinizing gelatin, may be used, and inorganic salts,
Anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (
For example, a sedimentation method (flocculation) using acylated gelatin, carbamoylated gelatin, etc. may be used.

Non-diffusible turnip 2 that reacts with the oxidized form of the color developing agent used in the present invention to produce a diffusible dye that bleeds the dye appropriately.
- represents a compound represented by the following general formula.

General formula Op+lLX where Op represents a diffusible coupler component that causes blurring and improves graininess of the INK color image.

X is a group that binds to the coupling position of the cabzi component and leaves by reaction with the oxidized product of the color developing agent, and has 8 to 32 carbon atoms.
It is a component containing a ballast group. a represents 1 or 2.

Among the couplers represented by the above general formulas, couplers represented by the following formula are particularly preferred.

General formula 0) General formula (It) In the formula "I s R2e J and 几 may be the same or different, hydrogen atom, halogen atom, alkyl group (
For example, methyl group, ethyl group, isopropyl group, and droxyethyl group), alkoxy group (such as methoxy group,
ethoxy group, methoxyethoxy group, etc.), aryloki group (for example, phenol group, etc.), acylamino group (for example, acetylamino group, trifluoroacetylamino group, etc.).

Sulfonamino groups (for example, methanesulfonamide groups, benzenesulfonamino groups, etc.), carbamoyl groups, sulfamoyl groups, alkylthio groups, alkylsulfonyl groups, alkylcarbonyl groups.

Represents a frayed group, cyan group, carboxyl group, hydroxyl group or sulfo group. However, the total number of carbon atoms in R1%B2, a, and 几 does not exceed 10.

X' represents a group having a so-called ballast group having 8 to 32 carbon atoms which imparts non-diffusibility to the coupler, and which can be separated by coupling with an oxidized product of an aromatic primary amine developing agent. In detail, it can be represented by the following general formula) or the general formula (■).

General formula (support)) General formula (to) In the formula, AI-
represents a chlorine atom or an iodine atom.

B represents a nonmetallic atom group necessary to form an aryl ring or a heterocycle, and B represents a 5- or 6-membered group with 9 atoms.
Represents the non-gold kA atomic group necessary to form a member heterocycle. These rings may further be fused with an aryl ring or a heterocycle. D represents a palust group, and b represents a positive integer. When b is plural, D may be the same, more or different, and the total number of carbon atoms is 8 to 32. DFi-0
+.

-8-, -Coo-, -0ONH, -8o. NH-1-
It may contain a linking group such as NHOONH-, -802-, -Co-, -NH-.

Other preferred couplers in the general formula IC are represented by the following general formula ff), CVrI or (4).

General formula (V) General formula (2) General formula 5 has 7 acylamide groups (e.g. globanamide group,
(benzamide group), anil group (e.g. 2-chloroanilino group, 5-acetamidoanilino group) or ureido group (e.g. phenylureido group, butaneureido group)
, R7 and R7 each represent a halogen atom, an alkyl group (e.g. methyl group, ethyl group, 1rucokyl group (
methoxy group, ethoxy group), acylamino group (e.g. acetamido group, benzamide group), alkoxycarbonyl group (e.g. methoxycarbonyl group), N-alkylcarbamoyl group (e.g. N-methylcarbamoyl group), ureido group (e.g. N- methylureido group), cyan group, aryl group (e.g. phenyl group, naphthyl group) N
, N-dialkylsulfamoyl group, nitro group, hydroxy group, carboxy group, aryloxy group, etc., f is an integer of 0 to 4, f is 2
In the above case, the filters 6 may be the same or different. However, in the general formula (Vl and individuals), 几, and f R6, the general formula (
In (b), the total number of carbons contained in R6 and R does not exceed 10. X'' is the following general formula (4), (g) and (X)
represents.

General formula (4) General formula (goods) -8- 几.

General formula (X) General formula (4) and (in Shu, 几) are general formula (V) ~
(l+1) is a group selected from the substituents listed in 1
When g is 2 or more, 几, Fi can be the same or different <, g
The total number of carbon atoms contained in each FL is 8 to 32.

几represents a substituted or unsubstituted alkyl group (e.g., pudyl group, dodecyl group, etc.), an aralkyl group (e.g., benzyl group, etc.), an alkenyl group (e.g., allyl group, etc.), or a bulk alkyl group (e.g., cyclopentyl group, etc.), Examples of the f substituent include a halogen atom, an alkoxy group (eg, butoxy group, dodecyloxy group, etc.), and an acylamino group (eg, acetamido group, nato-2-dicanamide group, etc.).

Alkoxycarbonyl group (such as a tetradecyloxycarbonyl group), N-alkylcarbamoyl group (such as an N-dodecylcarbamoyl group), L/ide group (such as a 2-decyl clay group), and a cyano group.

IJ-ru M (phenyl group), nitro group, alkylthio group (dodecylthio group, etc.), alkylsulfinyl group (tetradecylsulfinyl M-1k), alkylsulfone group, anilino group, sulfonamide group (hexadecanesulfonamide) The total number of carbon atoms contained in RIl is 8 to 32.

Among the combinations represented by the general formulas, preferred ones are represented by the following general formulas (to) and (to).

General formula (to) General formula (to) R3 is a hydrogen atom, an aliphatic group having up to lθ carbon atoms (for example, an alkyl group such as methyl, inglovir, acyl, cyclohexyl, octyl, etc.), an alkoxy group having up to 10 carbon atoms (for example, methoxy , impropoxy, pentadecyloxy, etc.), aryloxy groups (e.g. phenoxy group, p-tart-phterphenoxy7 group) linear formula (xII
) to (XV), or a carbamoyl group represented by the following formula (XM) K.

-NH-Co-G (Xffi)-NH-
8o□-G (XF/)-NH(3ONH
-G (XV) In the formula, G and G' may be the same or different, and each is a hydrogen atom (However, G and G' are not hydrogen atoms at the same time, and the total number of carbon atoms of G and G' is is 0, an aliphatic group having 1 to 12 carbon atoms,
Preferably, a straight chain or branched alkyl group or a cyclic alkyl group having 4 to 10 carbon atoms (eg, cyclopropyl).

cyclohexyl, norbornyl, etc.), or an aryl group (eg, phenyl group, 7-tyl group, etc.). Here, the above alkyl group and aryl group are halogen atoms (for example, fluorine, chlorine, etc.).

Nitro group, cyano group, hydroxyl group, carboxy group, amine group (e.g. 72) group, alkylamino i, dialkylamino group, anilino group, N-alkylanilino group, etc.) S alkyl group (e.g. as mentioned above), aryl groups (e.g. phenyl group, acetylaminophenyl group, etc.), alkoxycarbonyl groups (e.g. butyloxycarbonyl 2
1! F na g).

Acyloxycarbonyl group, amide group (e.g. acetamide group, methanesulfonamide group, etc.).

imide group (e.g. succinimide group etc.), carbamoyl M (sidelight tfN, N-diethylcarbamoyl group etc.), sulfamoyl group (e.g. N,N-diethylsulfamoyl group etc.), alkoxy group (e.g. ethoxy group, butyloxy (eg, phenoxy group, methylphenoxy group, etc.), aryloxy group (eg, phenoxy group, methylphenoxy group, etc.). In addition to the above-mentioned substituents, 几 may contain commonly used substituents.

FLlo is selected from a hydrogen atom, an aliphatic group having 12 or less carbon atoms, an alkyl group having 1 to 10 carbon atoms per %, or a carbamoyl group represented by the general formula (XW).几、□ 几、
% Lua 1.几, 4, and RI6 are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl211! is alkoxy group, alkylthio group, heterocyclic group, amino group, carbonamide! , sulfonamide group, sulf7amyl group.

Or represents a carbamyl group. R11 specifically represents any of the following groups: hydrogen atom, halogen atom (e.g. chloro, brome, etc.)
, the first with 1 to 12 carbon atoms.

Secondary or tertiary alkyl groups (511 e.g. methyl, propyl, inglovir, n-butyl, nibutyl, tert-butyl, hexyl, dodecyl, 2-chlorobutyl, 2-hydroxyethyl, 2-phenylethyl, 2-(2 ,4,6
-)lichlorophenyl)ethyl, 2-aminoether, etc.), alkylthio groups (e.g. octylthio group, etc.)
, aryl group (e.g. haphenyl, 4-methylphenyl, 2
, 4.6-)lichlorophenyl, 3.5-dibromophenyl, 4-trifluoromethylphenyl, 2-)lylfluoro-amethylphenyl, 3-trifluoromethylphenyl, 7-ter, 2-chloronaphthyl, 3-ethelnaphthyl etc.), heterocyclic groups (e.g. benzofuranyl group,
7 ranyl group, thiazolyl group, benzothiazolyl group, 7
tothiazolyl group, oxacylyl group, penzochytegryl group, nandooxacylyl group, pyridyl group, quinolinyl group, etc.), amine group (e.g. amino, methylamino, diethylamino, dodecylamino, phenylamino, tolylamino, 4-cyanophenylamino, 2 -trifluoromethylphenylamino, benzothiazolamino, etc.), carbonamide groups (e.g. ethylcarbonamide,
Alkylcarbonamide groups such as decylcarbonamide, etc.: phenylcarbonamide% 2,4.6-)lichlorophenylcarbonamide, 4-methylphenylcarbonamide, 2-eth)-? diphenylcarbonamide,
Arylcarbonamide groups such as naphthylcarbonamide, etc.: theazolylcarbonamide, penzothiazolylcarbonamide, naphthotealylcarbonamide.

Heterocyclic carbonamide groups such as oxtezolylcarbonamide, benzoxacylylcarbonamide, imidazolylcarbonamide, benzimidazolylcarbonamide, etc.), sulfonamide groups (e.g. pudelsulfonamide, dodecylsulfonamide), phenyl Alkylsulfonamide groups such as ethersulfonamide; phenylsulfonamide, 2,4.6-)lichlorophenylsulfonamide, 2-methoxyphenylsulfonamide,
Arylsulfonamide groups such as 3-carboxyphenylsulfonamide, naphthylsulfonamide, etc.; heterocyclic sulfones such as thiazolylsulfonamide, benzothiazolylsulfonamide, imidazolylsulfonamide, benzimidazolylsulfonamide, pyridylsulfonamide, etc. % sulfamyl group (e.g., alkylsulfamyl group such as globilsulfamyl, octylsulfamyl, etc.; phenylsulfamyl, 2,4
．． 6-) Lichlorophenylsul 7-amyl, 2-meth)-+
Like diphenyl sulfamyl, sulfate sulfamyl, etc. 7-aryl sulfamyl group; deazolyl sulfamyl,
heterocyclic sulfamyl groups such as benzothiazolylsulfamyl, oxazolylsulfamyl, benzimidazolylsulfamyl, pyridylsulfamyl groups, etc.) and alkyl groups such as carbamyl groups (e.g. ethylcarbamyl, octylcarbamyl, etc.) Carbamyl group: phenylsulfone h, 2,4.6-)')lArylcarbamyl group such as lorophenylcarpamyl; thiazolylcarbamyl, benzothiazolylcarbamyl, oxacylylcarbamyl, imifl ). R1□, R11% RI4 and RI5 can also include those listed in detail in R1, respectively, and J represents a nonmetallic atom necessary to form a 5- and 6-membered ring as shown below. . Namely, benzene ring, cyclohexene ring, cyclopentene ring, thiazole ring, oxazole ring, imidazole ring, pyridine ring, pyrrole ring, etc. Among these, a benzene ring is preferred.

x" has a group having 8 to 3z carbon atoms, -〇-1-3+, -
N=Represents a group that is bonded to the coupling position via N- and is capable of fogging with and leaving the oxidized product of an aromatic-grade amine developing agent. Preferably carbon is further -0-1-8-1-N
H-, -0ONH-1-COO-1-80□NH-, -
3O-1-SO2-.

You can stay there. Furthermore, these groups are -000H.

-3O3H, -0)1. It is preferable that #PK contains a group that is separated by alkali such as -8O2NH2. Also 几0
%R1゜*R11% R1□, R13, 几, 4.几、
5. By combining xh', it is possible to make the coupler substantially diffusion resistant.

Preferred specific examples of couplers that form a dye in which the dye produced by the coupling reaction represented by the general formula bleeds appropriately are as follows.

Yellow coupler] NO□ C00C12H25 Y-5 0.4H290 H3 05H,1(t) Y-14 [Magenta coupler] t M” 004H9H3 t 0CH.

M-10 at NHOOOH.

(Cyan coupler) 00HC, □H25 00H 0CH2CH2SCHC, 2N.

OOH 0CH2CH2SCHC,□H25 OOH H 00HO,,)I 2゜■ OOH H 00H2CH2SCjHO,□H25 OOH Q-7 H H 00HC1□H25 00H SCHO12H25 Coo) ( -tOH 3OHO,,H25 00002H5 00H0,2H25 OOH H H OCR2C !H2S0HOL2H2゜OOH H OCH20H,5CHOL2H2s C!OOH H 00H20H2SCHO, □H2!S 0OH 5, -17 H OCH2CH2SCHCj, □H25 00H 0H 0OH cooa, □HyoO H COOOH2C!HC8H1゜OH COOO,H25 The yellow coupler and magenta Exemplary coupler compounds are U.S. Pat. No. 4,264,723, U.S. Pat.
No. 54, No. 4,310,619, No. 4.301゜23
No. 5, JP-A-57-4044, JP-A-56-126833, JP-A-50-122935, etc.

Moreover, the compound 0-1-19 is disclosed in Japanese Patent Application Laid-open No. 56-193.
It can be easily synthesized by the method described in No. 8, No. 57-3934, No. 53-■05226, etc.

The amount of the non-diffusible coupler to be added, which reacts with the oxidized form of the color developing agent used in the present invention to form a diffusible dye with appropriate dye bleeding, ranges from o, oos mole per #&1 mole.
2 mol is preferable, more preferably 0.01 mol to 0.01 mol.
05 mol.

The silver halide emulsion of the present invention includes silver halides other than those of the present invention, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Any materials used in ordinary silver halide emulsions, such as silver chloride and silver chloride, can be used in combination.

Silver halide grains that can be used in combination with the silver halide emulsion of the present invention may be those obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the N particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the PH and pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.

The silver halide emulsion that can be used in combination with the present invention is manufactured by controlling the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains using a silver halide solvent as necessary. be able to.

Examples of the silver halide solvent include ammonia, thioether, thiourea, thiourea derivatives such as 4-substituted thiourea, and imidazole derivatives. Regarding thioethers, see U.S. Pat. No. 3,271,157, U.S. Pat.
．． 3. ! No. 17, No. 3,574,628, etc. can be referred to.

When the solvent is other than ammonia, the amount of the solvent to be used is 1X10-' to 1. oi [amount %, especially 1×10−1
~IXLQ-'wt% is preferred. In the case of ammonia, it can be selected arbitrarily.

Silver halide grains that can be used in combination with the silver halide emulsion of the present invention include cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts containing), rhodium salts, Metal ions can be added using at least one selected from salts (including lead salts) and iron salts (complex salts including) to contain these metal elements inside the particles and/or on the surface of the particles, Further, by placing the particles in an excessively reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or the salts may be left in the silver halide emulsion. When removing the salts, Research Disclosure
Closure) No. 17643.

The silver halide grains that can be used in the silver halide emulsion of the present invention may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the grain interior and the surface layer. There may be.

The silver halide grains that can be used in combination with the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains that can be used in the silver halide emulsion of the present invention may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or irregular crystal shapes such as spherical or plate shapes. It may also have a crystalline form.

In these particles, the (l Q O) plane and the (l L
l) Any surface ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size (grain size represents the diameter of a circle with an area equal to the projected area) of the silver halide grains that can be used in combination with the present invention is preferably 5 μm or less, and particularly preferably 3 μm.
m or less.

Silver halide emulsions that can be used in combination with the present invention may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used.

The monodisperse emulsion referred to herein is as described above. ) may be used alone or in combination. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used together.

The silver halide emulsion that can be used in combination with the present invention may be a mixture of separately formed silver halide emulsions of 2N or higher.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after the end of chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
Hydrophilic colloids such as synthetic hydrophilic polymer substances such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and single or copolymers can also be used.

When gelatin is used as a binder (or protective colloid) for the silver halide emulsion of the present invention, the jelly strength of the gelatin is not limited, but the jelly strength is 250 g or more (
The value measured by the buggy method) is preferable.

The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention have binder (or protective colloid) molecules arranged in a beam structure to increase film strength. Hardening can be achieved by using one kind or 2N or more of a film agent. “!i!!m agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution. be.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. be able to.

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-)22-diamine derivatives, aminophenol derivatives, etc.) during color development processing. A dye-forming coupler is used that acts to form a dye.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. At least one of these couplers is
selected from the couplers of the invention. However, depending on the purpose, photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is acceptable. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, colorants, and 8! Compounds that release photographically sensitive fragments such as film agents, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers can be included. These dye-forming couplers may be used in combination with colored couplers that have a color correction effect or DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DiR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Although a coupling reaction is carried out with an oxidized form of an aromatic primary amine developer, a colorless coupler that does not form a dye can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color cast inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water-soluble one as necessary. Dissolve using a secondary solvent and use a surfactant in a binder (or hydrophilic colloid) such as an aqueous gelatin solution to disperse using a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. After emulsifying and dispersing the colloid, it may be added to the desired hydrophilic colloid layer.

A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

In the present invention, the ratio of high boiling point organic solvent to low boiling point organic solvent is 1:0°1 to L:50, more preferably 1:1 to 1:2.
Preferably, it is 0.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color fog preventive agents, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants and nonionic surfactants can be used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using organic or ultrasonic waves. , cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the light-sensitive material of the present invention, causing color turbidity and deterioration of sharpness. In addition, a color cast inhibitor can be used to prevent graininess from becoming noticeable.

The iron color antifogging agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer that prevents deterioration of dye images can be used in the light-sensitive material using the silver halide emulsion of the present invention.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material of the present invention.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change developability such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention. . Compounds that can be preferably used as development accelerators are listed in Research and Disclosure+
(Research Disclosure) 17643
The development retardant is a compound described in Section XXIIIJE of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of a light-sensitive material using the silver halide emulsion of the present invention may contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorpholine for the purpose of increasing sensitivity, increasing contrast, or promoting development. , quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, etc.

In the light-sensitive material using the silver halide emulsion of the present invention, a fluorescent whitening agent can be used for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable.

A light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used as a hydrophilic colloid other than the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. It may be used in layers.

The photographic emulsion N and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
For the purpose of preventing static electricity, improving slipperiness, emulsification dispersion, preventing adhesion, improving photographic properties (promotion of development, hardening, sensitization, etc.), etc.
A variety of surfactants can be used.

The support used in the photosensitive material using the silver halide emulsion of the present invention is a flexible reflective material such as paper laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene co-electrode), or synthetic paper. Supports, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, flexible supports with reflective layers on these films, and glass. , metals, ceramics, etc.

The photosensitive material of the present invention can be used directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, or adhesion of the surface of the support.1. It may be applied via a subbing layer of tm or higher to improve antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties.

When coating a light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties.

Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will cause gelation in the coated area, it is best to mix them using a static mixer or the like just before coating. preferable.

In preparing the photosensitive material using silver halide of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers are prepared through research and disclosure.
It can be applied by the method described in Section A of XV of Disclosure No. 17643, and dried by the method described in Section B1 of Disclosure No. 17643.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any light emitted from a phosphor excited by X-rays, γ-rays, α-rays, etc. can be used.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

Various color developments can be used for the development of the photosensitive material of the present invention. Alternatively, a color image may be formed by an inversion method. When using the reversal method, a black and white negative development process is performed and white exposure is given without a fixing process, or a color development process is performed after processing with a bath containing a fogging agent.
(The processing step of providing white light exposure or the step of processing with a fogging agent may be the same as the color development processing step.) Each processing step is usually carried out by immersing the photosensitive material in a processing solution. For example, a spray method in which the treatment liquid is supplied in the form of a spray, a web method in which the treatment is brought into contact with an assembly impregnated with the treatment liquid, a viscosity treatment method, etc. may be used.

The color development process includes a color development process, a bleaching process, a fixing process, a water washing process if necessary, and/or
Alternatively, the stabilization process is performed, but instead of the process using a bleach solution and the process using a fixer, a bleach-fixing process can be performed using a -bath bleach-fix solution;
It is also possible to perform a monobath processing step using a one-bath development, bleach-fix processing solution that allows color development, bleaching and fixing to be carried out in one bath.

In combination with these treatment steps, a pre-hardening treatment step, its neutralization step, a stop-fixing treatment step, a post-during treatment step, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the light-sensitive material and the development process is performed using an activator solution, or instead of the monobath process. The activator treatment, bleaching, and fixing treatments may be performed simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as a final step, either a water washing process, a water washing alternative stabilization process, or a stabilization process accompanied by a water wash process.) - Color development process - bleaching process - constant fixation process - Color development process - Bleach-fixing process / Pre-treatment film process - Neutralization process - Color development process - Stop-fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process Processing process/Color development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process/Monobath process/Activator process - Bleach-fix process/Activator process - Bleaching Processing process Constant fixation processing process In addition to these treatments, there is a method in which the developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification) described in JP-A No. 58-154839. Processing may be performed using a developing method that increases the amount of dye produced, such as processing.

[Example] The present invention will be further explained below with reference to Examples.

Example l A, Preparation of Comparative Emulsion I-1 ■ Preparation of silver iodobromide grains for A phase (inner core) 30 g of gelatin, 8 g of potassium bromide, 0.1% 3.4-dimethyl-4 in 1 bottle of water - Add 80 tal of methanol solution of thiazoline-2-thione and place in a container kept at 75°C without stirring.Aqueous solution containing 250 g of silver nitrate per sentence (liquid A) 8
00ml and 780ml of an aqueous solution (solution B) containing 5g of potassium iodide and 206g of potassium bromide per sentence.
They were simultaneously added by double jet method over 60 minutes while maintaining r 1.41. The thus obtained silver halide grains have a size defined by the projected area diameter (the same applies hereinafter) of 0.91 gm, and are octahedral silver iodobromide grains containing 2 mol % of silver iodide.

■ Growth of phase C (coating layer) 34g of silver and 7901 g of water from the phase A emulsion described in ■ above.
15g gelatin, 0.1% 3.4-dimethyl-4
- Mix 80% of a methanol solution of thiazoline-2-thione and place it in a container kept at 75°C while stirring.
4N AgN0ff solution 650+al and 1.09N K
Br solution 6SOIlu was simultaneously added by double jet method over 50 minutes while maintaining par 1.41. The silver halide grains thus obtained have an average diameter of 1.
They are monodispersed octahedral particles of 45 hm, and structurally have a core-shell structure consisting of an A phase and a C phase of pure silver bromide.

The halogenated emulsion thus obtained was treated with 10-' mol of chloroauric acid 6X per mol of silver and 1.3X of thiosulfuric acid sorter.
After adding 10-5 mol and chemically ripening at 60°C for 60 minutes, 4-hydroxy-6-methyl-1,3
,3a,7-chitrazaindene was added in 3X 10-'' moles.

Is the adjustment method for Comparative Emulsion B n-1 and Emulsions ll-2 to ■-7 of the present invention equivalent to that of Comparative Sample I-1? On the other hand, KI at 75℃
Phase B was introduced by adding 100 ml of aqueous solution over 10 minutes with sufficient stirring, and then phase C (second N!a) of pure silver bromide was added, resulting in a monodisperse of 45 p-*. Octahedral particles were obtained. The amount of K used per 100 m aqueous solution is 0
．． 1g, 0.2g, 0.1g, 0.4g
, 1.0g, and 2.0g respectively as sample ll-1.
, ■-2, ll-3, rl-4, ll-5, and ■-6.

However, the process conditions after chemical ripening were the same as those for comparative emulsion I-1.

Adjustment table of silver iodobromide in which phase B (first coating phase) was introduced by substitution method with iodine ions Mole fraction of phase B (when phase IB was introduced by substitution with iodine)
A phase AgBrI (I = 2 mo1%), B phase A
gI, C phase 11gBr; A phase/C phase (1) Silver t ratio =
1/3) Growth of the C phase (coating layer) of silver iodobromide prepared in C comparative emulsion 1-2 In addition to the A phase prepared in (1) of comparative emulsion I-1, C of comparative emulsion 1-1 (2) was added. Kf was added to 550 ml of 1.09 N KBr solution instead of the 1.09 N KBr solution used for phase growth.
:1. : The C phase was grown using a solution mixed with Ig, and the silver iodide content in both the A phase and the C phase was uniformly 2 mol%.
A comparative sample of 1° C.m octahedron was obtained.

D The adjustment method for the silver iodobromide emulsions n-7 to H-11 of the present invention into which the B phase (first coating layer) of silver iodide is introduced is the same as that of the above-mentioned comparative emulsion 1-2. silver amount 3 before moving on to the growth of
100 Kl aqueous solutions with different concentrations for 4 g of A phase emulsion
mM was added at 75° C. for 10 minutes to grow a silver iodobromide C phase having roughly the same composition as the A phase. In this way, monodisperse octahedral silver halide grains with a grain size of 1.4 gtm were obtained. Chemical sensitization was carried out under the same conditions as for comparative emulsion 1-1 to prepare emulsions r[-7 to -11.

Table 2 Molar fraction of phase B when Kr solution and equivalent amount of W seedling solution were simultaneously introduced (A phase, C phase both AgBrI
(I = 2 mo1%), B phase Agr; silver molar ratio of A phase/C phase = I:3) E Emulsions II-12 to ■-16 of the present invention and comparative emulsion I-3 in 1M of adjusted water Gelatin 30g, potassium bromide 0.4g, 2
Add 30 JL of 5% ammonia water and place in a container kept at 50°C while stirring 13 ml of an aqueous solution (liquid A) containing 250 g of silver nitrate per sentence and 1! After simultaneously adding 13 tl of an aqueous solution (liquid B) containing 180 g of potassium bromide per liter for 1 minute, to 187 cl of liquid A,
In order to keep the solution at pBr = 2.44, they were simultaneously added using the potential control method (phase A, i.e., the internal core), and then a 200 mM aqueous solution of potassium iodide was added over 20 minutes with sufficient stirring to form the phase B (phase A). A phase C (second coating layer) is introduced in the same process as phase A, and a phase C (second coating layer) is introduced.
．． 56 gm of monodisperse cubic particles consisting of phase A and phase C were obtained. The amount of Kl used in phase B was 0.05g, 0.1g, 0.2g, 0.3g, 0 per 2001ml aqueous solution.
．． Emulsions ■-12 to ■-16 were obtained by changing the emulsions to 4 g. In addition, as a comparative emulsion, an emulsion to which the I solution was not added was prepared (comparative sample Nee 3). The silver halide emulsion thus obtained was added with 1.9 chloroauric acid per mole of silver.
x 10-8 mol and 4 x 10-' mol of sodium thiosulfate were added, and chemical ripening was performed at 55°C for 60 minutes.

Table 3 Molar fraction of phase B when phase B is introduced by iodine substitution (A phase, C phase both AgBr; B phase AgI: molar ratio of A phase/C phase = 1/3. Crystal habit: cubic) F Comparison of Emulsions I-17 to n-19 of the Present Invention Emulsion I
Silver iodobromide grains for the A phase (inner core) were prepared in the same manner as in -1. However, after adjusting the addition time and setting the size to 0-471L+a, an aqueous solution of KBr + Kl and KBr +
AgN0 equivalent to KI. An aqueous solution was simultaneously added using a potential control method to introduce a B phase (first coating layer) having a total silver content of 55 mol %. At that time, the ratio of Kl and KBr was changed. About each emulsion.

Emulsions 1-17 to 11-19 were prepared by forming a C phase (coating phase) in the same manner as comparative emulsion I-2 and carrying out the following steps of chemical ripening. However, the addition time was adjusted so that the total amount of silver in phase C was 31.3 mol %. The silver halide grains used here were monodisperse octahedral grains with a size of 1.4 #LI11.

Table 4 Silver iodide mole fraction of phase B when phase B is AgBrI (both A phase and C phase AgBr1 (I = 2a+o
1%): mol% of silver in phase A = 3.7 mol%, mol% of silver in phase B = 65 mol%, mol% of silver in phase C = 31.3 mol%) G Comparative emulsion V-1 and emulsions of the present invention ■-20 to ■
30 g of gelatin, 8 g of potassium bromide, 0.0 g of potassium bromide, 141 g of adjusted water of -23.
Add 80 tal of a 1% methanol solution of 3,4-dimethyl-4-thiazoline-2-thione and place in a container kept at 75°C while stirring.An aqueous solution containing 250 g of silver nitrate per sentence (Liquid A) 2QO tall and per IIL. An aqueous solution containing 5 g of potassium iodide and 206 g of potassium bromide (B
Liquid) 200 complexes were simultaneously added by double jet method over 16 minutes (A phase, ie, inner core).

Next, add a 100mM Kl aqueous solution for 10 minutes while stirring thoroughly.
Introducing phase B, that is, the first coating layer, by adding in portions,
Thereafter, 600 μl of liquid A and 600 μl of liquid B were simultaneously added over 45 minutes by a double jet method (phase C, ie, second coating layer). The silver halide grains thus obtained are octahedral silver iodobromide grains of 0.91 p, m.

The amount of Kl used for B phase formation was 0 per 100 mM aqueous solution.
．． The emulsions were changed to 1 g, 0.2 g, 0.4 g, 0.8 g, and 1.6 g to give emulsion ■-20 to low 23, respectively. In addition, an emulsion without the introduction of iodine was used as a comparative emulsion for Emulsion Process-4. However, the process conditions below chemical ripening are comparative emulsion I.
-1, or during chemical ripening, per mole of silver, 1.2 x 10-' mole of chloroauric acid, 2 mol of sodium thiosulfate.
．． 6X 10-' moles were used.

Table 5 Molar fraction of phase B when phase B is introduced by iodine substitution (A phase, C phase both AgBrI (I = 2 mo1%) 2 B phase Ag1. Molar ratio of A phase/C phase = 1/3; 0.
91 uLm Octahedral) Preparation of H sample A color photosensitive material sample consisting of two layers having the composition shown below was prepared on a polyethylene terephthalate film support according to a method known in the art.

First layer silver iodobromide emulsion Amount of silver coated in the emulsion as shown in the table: 2.2 g/rn' Coupler Coupler as shown in the table: 0.25 g/rn'
rn' DIR Compound 1 5X per mole of silver 10-
'Mole (When using the Y-number coupler shown in the example, do not use a colored coupler. When using an M-number coupler, use CM-1 as the colored coupler, and use a C-number coupler. When using CC-1 as a colored coupler, the amount added is 1 silver.
2.8X1'0-gomoles to moles. ) 2nd layer gelatin layer dry film thickness 0.8gmDIFt
Compound 1 In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.

In addition, the compounds used to make the samples are as follows.

Sensitizing dyestuff: Anthro-5,5'-dichloro-3,3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxyte pyridium salt sensitizing dye ■: Anhthro 9-ethyl: l, 3''-di(γ-sulfopropyl)-4, S, 4 ",S"-dibenzothiacarbocyanine hydroxide/triethylamine salt gelatin hardening agent 0M-1 ρt to-1 These samples 1 to 8 were subjected to wedge exposure or sine exposure in a conventional manner, and then subjected to the following development treatment. I did it.

Processing process (38°C) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water
3 minutes 15 seconds fixing 6 minutes 30 seconds water washing 3 minutes 15 seconds stabilizing bath 1 minute 30 treatments The composition of the treatment solution used in the treatment process was as follows.

[Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-
Hydroxyethyl) - Aniline sulfate 4.75g Anhydrous sodium sulfite 4-25g Hydroxyamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide
1.3 g nitrilotriacetic acid trisodium salt (1 hydrate) 2.5 g potassium hydroxide 1.0 g Add water to make one sentence, and adjust to pH 10.0 using potassium hydroxide.

[Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Permanent acetic acid
Add 10.0+a water to make one sentence, and adjust the pH to 6.0 using ammonia water.

[Fixer Composition] Ammonium thiosulfate 50% aqueous solution 162L x 1 sentence Anhydrous sodium sulfite 12.4 g Water was added to make one sentence, and the pH was adjusted to 6.5 using acetic acid.

[Stabilizing liquid composition] Formalin 37% aqueous solution 5.0 @Mikonidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 + Add a Bunsui to make one sentence.

The density of the obtained magenta dye image was measured through a magenta filter, and the fog, relative sensitivity (S), and maximum density (O to ax) were calculated, and the obtained results are shown in Tables 6 to 10.

Note that detection of the sharpness improvement effect of one image is performed using MTF (Mod
ulation Transfer Function
) and compared the MTF sizes for spatial frequencies of 30 trees/1lIIl.

RMS is 10 of the standard deviation of density value fluctuations that occur when a dye image with a dye image density of D ain + 0.8 is scanned with a microdensitometer with a circular scanning aperture of 251 L.
00 times value was shown.

Here, coupler M t coupler 0 As is clear from Tables 6 to 10, it can be seen that according to the present invention, both graininess and sharpness are improved.

Claims (1)

[Scope of Claims] It has at least one silver halide emulsion layer on a support, and 10% (weight) or more of the photosensitive silver halide grains present in the silver halide emulsion layer are bromide. An inner core made of silver or silver iodobromide, a first coating layer made of silver iodide or silver iodobromide on the outside of the inner core, and a further coating layer of silver bromide or the first coating layer on the outside of the first coating layer. In silver halide grains having a ratio of projected area diameter to thickness of less than 5 and consisting of a second coating layer made of silver iodobromide having a different halide composition, (1) Iodine content of the first coating layer is 10 mol% or more higher than the iodine content of the inner core, and (2) in the silver halide emulsion layer, the ratio of silver in the first coating layer to the entire grain is 0.01 to 90 mol%. A silver halide photographic light-sensitive material characterized by containing a non-diffusible coupler that reacts with an oxidation product of a color developing agent to produce a diffusible dye that causes the dye to bleed appropriately.