JPH03194540A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity and hardly causing fog by forming particles in a silver halide emulsion layer in the presence of an oxidizing agent for silver and carrying out chemical sensitization in the presence of thiocyanate or selenocyanate. CONSTITUTION:An inorg. oxidizing agent such as ozone or hydrogen peroxide or an org. oxidizing agent such as quinone is added during the formation of particles in a silver halide emulsion to convert fine silver atoms into silver ions and then chemical sensitization is carried out in the presence of at least one kind of thiocyanate such as NaSCN or NH4SCN or at least one kind of selenocyanate such as NaSCN or NH4SeCN. A sensitive material having high sensitivity and hardly causing fog is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material that is highly sensitive, has little capri, and has excellent stability over time. .

[Conventional technology]

Recent technological trends in silver halide photographic materials include, for example, in the field of color photographic materials, We pursue photosensitive materials that have graininess, sharpness, and color reproducibility that can satisfy even high-sensitivity photosensitive materials and photosensitive materials used for shooting with small format cameras such as the 110 size system and disk size system. The direction is to continue.

On the other hand, as photography opportunities become more diverse and versatile, it has become increasingly important to improve the problems such as increase in capri, decrease in sensitivity, and deterioration of graininess due to aging of photosensitive materials from the time they are manufactured to the time they are used. It's coming.

Technology to increase the sensitivity of silver halide emulsions is also a major source of grain improvement in that it is possible to achieve the same sensitivity with smaller grains.

Conventional chemical sensitization methods for increasing the sensitivity of silver halide photographic emulsions include sulfur sensitization, selenium sensitization, noble metal sensitization, reduction sensitization, and hydrogen sensitization. are used alone or in various combinations. These sensitization methods are described in the book by T.H. James [The Theory of the
Photographic Process J (The Theor
y of the PhotographicProc
ess) 4th edition (Macmillan Co, 197
7 years) on pages 149-160 and 164-165.

Furthermore, in addition to these aggravating methods, various emulsion manufacturing methods using silver halide solvents or so-called stabilizers have been proposed as techniques for increasing sensitivity. Furthermore, many methods of performing chemistry in the presence of these compounds have been investigated.

Chemical sensitization in the presence of a thiocyanate compound, which is a common silver halide solvent, was disclosed in JP-A-63-15.
1618, etc. A photographic material using a silver halide photographic emulsion prepared by such a method achieves high sensitivity, but the problem is that the capri increases significantly after storage over time. Colier (Korea) is J
our own of ImagingScience
Vol. 31, page 135 (1987) states that silver halide emulsions containing surface silver nuclei form fog centers in the presence of thiocyanide, and the above phenomenon is also due to the presence of silver nuclei introduced on the grain surfaces. It can be assumed that this is caused by However, no concrete method has been found to date to achieve high sensitivity while suppressing the increase in Capri.

(Object of the Invention) An object of the present invention is to provide a photographic material with high sensitivity and less fog.An object of the present invention is to provide a photographic material with high sensitivity and less fog. In addition to the above objects, another object of the present invention is to provide a photographic material with excellent storage stability.

[Means for solving problems]

The above objects have been achieved by the silver halide photographic materials described in (1) to 4) below.

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer is formed into grains in the presence of at least one oxidizing agent for silver; A silver halide photographic material comprising a silver halide emulsion chemically sensitized in the presence of at least one of thiocyanate and selenocyanate.

(2) The oxidizing agent for w & is of the formula (+) or In)
The silver halide photographic material according to claim 1, which is at least one compound represented by any one of the following.

(1) R-3o! S-M (II) R-soo S-M (II) R5OtS L-5SOz R”
In the formula, R, R1, R'' may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is O or l.

The compounds of general formulas (1) to (III) may be polymers containing divalent groups derived from the structures shown in (1) to (III) as repeating units, and when possible, , R, R1, and R''L may be bonded to each other to form a ring.

(3) A silver halide emulsion comprising silver halide grains having a silver iodide content of 1 mol% or more and a silver bromide content of 50 mol% or more. 2) Any silver halide photographic light-sensitive material.

(4) The silver halide photographic light-sensitive material according to claim (3), which is a silver halide grain having a silver iodide content on the surface of the grain of 5 mol % or more.

The present invention will be explained in detail below.

The manufacturing process of silver halide emulsions is roughly divided into the steps of grain formation, desalting, redispersion, and chemical sensitization. Zero grain formation is divided into nucleation, ripening, growth, and the like. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated.

The timing of adding the oxidizing agent to the silver of the present invention must be selected during grain formation. The preferable effect of the present invention cannot be obtained by adding it in the desalting step or chemical sensitization step after the completion of grain formation, or in the chemical sensitization step.

The oxidizing agent for silver in the present invention refers to a compound that acts on metallic silver to convert it into silver ions.In particular, it converts extremely minute silver atoms, which are produced as by-products in the process of forming silver halide grains, into silver ions. Compounds that cause this conversion are effective. The silver ions generated here may form silver salts that are poorly soluble in water, such as silver halide, silver sulfide, and silver selenide.
Also, a water-easily soluble silver salt such as silver nitrate may be formed.

The oxidizing agent for silver may be inorganic or organic. Inorganic oxidizing agents include ozone, hydrogen peroxide and adducts thereof (for example, NaBOz HzO
x ・3Ht 0,2NaCO3・3Hz Ot,
Naa Pg Oq ・2H* Ot, 2Nat S
O4 Hz Ox 2Ht O), peroxylates (e.g. Kz St Ot , Kg Ct Oa,
Kt Pg Os ), peroxy complex compounds (e.g. Kz (T i (Ox ) Ct Oa ).
3) 1.0.4 Kg S Oa ・Ti (0riOH
・S04 ・2H20, Nas (VO(Ox)
(Ci Oa) t6H! O), permanganate (
For example, KM, O,), chromate (e.g., Kg C
Oxygen acid salts such as rz Ot), halogen elements such as youma and bromine, perhalogenates (e.g. potassium periodate), salts of high valent metals (e.g. potassium hexacyanoferric acid) and thiosulfonic acids. There is salt, etc.

Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromsuccinimide,
Chloramine T1 Chloramine B) may be mentioned as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonic acid salts, and organic oxidizing agents such as quinones.

A more preferred oxidizing agent is a thiosulfonate, which can be selected from compounds represented by formulas (1) to (III). Among these, the most preferred is the compound represented by formula (1).

(+) R-sow S-M (II) R-3o, 5-Rl (I[[) R-3o S-L, -3SO1-R
"In the formula, R, M, and R" may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0 or l.

Compounds of formulas (1) to (II) include (1) to (I
A divalent group derived from the structure shown in II) or (II)
It may be a polymer containing only two groups derived from the structure shown in I) as repeating units, and when possible, RSM, R'', and L may be bonded to each other to form a ring.

To explain in more detail the thiosulfonic acid compounds of formulas (1), (II) and (I[[), when R, M and Bt are aliphatic groups, saturated or unsaturated, linear, branched or A cyclic aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkynyl group having 2 to 22 carbon atoms, which may have a substituent. .

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R1 and R1 include monocyclic or condensed ring aromatic groups, preferably those having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, M and Rt is 3 to 1 having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium and having at least one carbon atom.
A 5-membered ring, preferably a 3- to 6-membered ring, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole,
Examples include imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadeazole ring.

Substituents for R, M and 2 include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, octyloxy), aryl groups (e.g. phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (e.g. fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy), alkylthio groups (e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl), sulfonyl groups (e.g. eva, methylsulfonyl, phenylsulfonyl), acylamino groups (e.g. acetylamino,
benzoylamino), sulfonylamino groups (e.g. methanesulfonylamine, benzenesulfonylamino),
Acyloxy group (e.g. acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, -3o
, 3M group, (M represents a monovalent cation) -SO□R1
The basics are given.

The divalent linking group represented by L is an atom or atomic group containing at least one selected from C, N, S and 0. Specifically, alkylene group, alkenylene group, alkynylene group, arylene group, 0- -3- -NH-
-CO--5o□ alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include (CHz+
(n=1-12), -cHt -CH=CH-CH! - CH, C=CCH.

It will be done.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (ammonium, tetramethylammonium, tetrabutylammonium, etc.), phosphonium ions (tetraphenylphosphonium), and guanidyl groups.

When formulas (1) to (III) are polymers, examples of the repeating units include the following.

Examples of the divalent aromatic group of L include phenylene group, naphthylene group, etc. (CI-C
H,9(:o,c)1. I(xc)l=so=s in cllgo
M.

Hs (C-CHr C0zCHzCHt S-3o! R CH.

(C-CH!) These polymers may be homopolymers or copolymers with other copolymerizable monomers.

Specific examples of compounds represented by formulas (i), (■), or (III) are listed in Table A, but the compounds are not limited thereto.

Compounds of formulas (1), (II) and (DI) are disclosed in JP-A-54-1019; British Patent No. 972,211;
al of Organic Chemistry (
Journal of Organic Chemistry) 53
Vol. 396 (198B) and Chemical A
bstructs (Chemical Apstructs) Volume 59,
It can be easily synthesized by the method described or cited in 9776e.

The oxidizing agent for silver of the present invention is preferably added in an amount of 101 to 1 mol per 1 mol of silver halide, and more preferably 10 to 10-2, particularly 10-' to 10-3 mol of Ag. amount is preferred.

The oxidizing agent for silver of the present invention can be selected from the above-mentioned compounds, and two or more kinds of compounds can be used in combination. Further, the addition position may be one or divided into two or more locations. In these cases, it is preferable that the total amount of the compound is within the range of the above-mentioned addition amount.

In order to add the oxidizing agents represented by formulas (1) to (III) during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

(I-1) (1-2) (I-3) (■-4) (Knee 5) (I-6) CI-7) CH, SO, 5N a C! HsS OzS N a Cs H? S Ot S K C,H,S O□5Li ChHI3SOzSNa csH+tsOzsNa (1B) C+oHt+5OzSNa (19)
C+zHzsS O! S N, aCZ 10) C+
aH3,5OxSNa(1-11) (1-12)t-C,H9SO! 5Na (I 13)
CHsOCHzCHzSOzS-Na(1-15) CHz =CHCH! SO2S Na (T-17
) (T-18) (I-19) (1 25) (I-26) (I-27) (1-28) (knee 20) (j-21) (L-22) (1-23) ( Knee 24) (I-29) KSSO□ (CH2)! So□5K (I-30) Na 5SOz (CH,) msO, 5Na (I-31) Na S S Oz (CH-) a S (c H2)
430! S Na CI-32) (L-33) (1-1) Cz Hs SO! S CH5(IL-2> Ca Hl, S Oz S CHz CHx(L-3) (Knee 4) ([-5) Cz Hs S Oz S CHz CHz CN(]
IL-6) C, H, SO! S CHCH,CN (In-12) (I[-13) (IL-14) DL-15) (π-8) (IL-10) (L-11) (TL-16) (TL-17) ( X-18) C,H,SO□S CH,CHzc HICH,OH(
II-19) (L-20) (7[”-21) CHas S 0X(CHz) as OzS CH3(
IL-1) (If-22) CHffS SO, (CH,)! SO! SCH3
(IL-23) ([-2) CxHsSOzSCHzCHzSO□CHzCHzSS
(hC!Hs(IIL-3) ('l-24) (L-4) CHzCHxOH -271 (molar ratio) (positive-25) (TL-5) ([-6> (l-7) ([- 8) (JL-9) C, H, S O The thiocyanate or selenocyanate used in the present invention is optional, such as Na5CN, Na5eCN, KS
C.N.

Alkali metal salts such as KSeCN, NH, and SCN.

Ammonium salts such as NHa 5eCN can be preferably used.

The compound is added until chemical sensitization has substantially begun. Specific addition timing includes a particle formation step, a desalting step, or a chemical sensitization step before adding a chemical sensitizer.

The amount of the compound added is 10-' per mole of silver halide.
It is preferable to add 10-1 mol from 10-1 mol.
% to 10-'', particularly 10-4 to 104 mol per mol of Ag is preferred.

The compound added may be one type or many types, and the addition position may be one or two or more. In these cases, the total amount of the compound is within the range of the above-mentioned addition amount. It is preferable.

Chemical sensitization in the presence of the compound can be carried out by the following method.

Chemical sensitization is described by Ding H. James,
The Photographic Process, 4th edition, Macmillan Publishing, 1977, (T, H, Jases+ Th
eTheory of the Photography
ic Process, 4th ed.

Mac*1llan, 1977), pp. 67-76, or with activated gelatin, as described in Research Disclosure, Vol. 120, 19.
April 1974, 12008; Research Disclosure, 34S, June 1975, 13452, U.S. Patent Nos. 2.642.361, 3,297.446, 3
, No. 772,031, No. 3゜857.711, No. 3,
901,714, 4.266.018, and 3,904,415, and British Patent No. 1,315,
pAg5-10. as described in No. 755. pH5～
8 and a temperature of 30 to 80° C. using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, or a combination of these sensitizers. Chemical sensitization is optimally performed in the presence of gold compounds and as described in U.S. Pat.
, 857,711, 4.266.018 and 4,054,457, or in the presence of sulfur-containing compounds such as hypo, thiourea compounds, and rhodanine compounds. The effects of the present invention are
This is noticeable when total sulfur sensitization is performed as chemical sensitization.

Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine.

Examples of chemical sensitization aid modifiers include U.S. Patent No. 2.131.0
No. 38, No. 3,411,914, No. 3゜554.75
No. 7, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The silver halide emulsion of the present invention comprises silver halide grains having a silver iodide content of 1 mol% or more and a silver bromide content of 50 mol% or more as an average composition of the entire grain. It is an emulsion. Other halide components are optional, but if the silver chloride content exceeds 50 mol%, the preferred effects of the present invention cannot be obtained.The preferred silver iodide content is 2.
The silver bromide content is 60 mol% or more. Further, particularly preferably, the silver iodide content is 3 mol% or more and 18 mol% or less, and the silver bromide content is 80 mol% or more and 97 mol% or less.

Particularly preferred silver halide emulsions of the present invention have a silver iodobromide phase with a silver iodide content of ~40 mol % inside the grains, and this silver iodide phase contains a lower amount of silver iodide. coated with silver halide, and the surface of the grain, i.e.
P S (X-ray Photo-electron
These are silver halide grains having a silver iodide content of 5 mol % or more up to a depth (approximately 10 A) analyzed by a surface analysis method (5 pectroscopy).

Regarding the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, please refer to "Electron Spectroscopy" by Atsushi Aihara et al. (Kyoritsu Library 16, published by Kyoritsu Shuppan, 1978). can do.

The standard measurement method for XPS is
This is a method of observing the intensity of photoelectrons (usually l-3 dyt, Ag-3 dS/l) of iodine ([) and silver (Ag) emitted from silver halide grains in a suitable sample form.

To determine the iodine content, a calibration curve of the photoelectron intensity ratio of iodine (1) and silver (Ag) (intensity (I) 7 intensity (Ag)) is calculated using several types of standard samples with known iodine contents. can be calculated from this calibration curve. In the case of a silver halide emulsion, XPS measurement must be performed after gelatin adsorbed on the surface of silver halide grains is decomposed and removed using a protease or the like.

The silver iodide content in the core and shell portions can be measured by X-ray diffraction. An example of applying X-ray diffraction to silver halide grains is given in H. Hirsch's Journal of Photographic Science Vol. 10 (1962), 12.
It is stated on pages 9 onwards. If the lattice constant is determined by the halogen composition, Brang's condition (2dsinθ−n
A diffraction peak occurs at a diffraction angle that satisfies λ).

Regarding the measurement method of X-ray diffraction, see Basic Analytical Chemistry Course 24 “X
It is described in detail in "X-ray Diffraction Handbook J" (Kyoritsu Shuppan) and "X-Ray Diffraction Handbook J" (Rigaku Denki Co., Ltd.). The standard measurement method is to use Cu as a target and obtain the diffraction curve of the (220) plane of silver halide using β rays as a radiation source (tube voltage 40 KV, tube current 60 mA).

In order to increase the resolution of the measuring device, the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed are selected appropriately and the measurement accuracy is confirmed using a standard sample such as silicon. There is a need to.

When we obtained a curve of diffraction intensity versus diffraction angle for the (220) plane of silver halide using β-rays for Cu, we found a diffraction peak corresponding to a high-iodine layer containing 10 to 45 mol% silver iodide and a low-iodide layer. There are cases where the diffraction peaks corresponding to the iodine layer are detected in a clearly separated state, and cases where they overlap each other and are not separated into two distinct peaks.

The method of decomposing a diffraction curve made up of two diffraction components is well known, for example, in Experimental Physics Course 11.
It is explained in books such as Lattice Defects (Kyoritsu Shuppan).

It is also useful to analyze the curve using a curve analyzer manufactured by DuPont, assuming that the curve is a Gaussian function or a function such as a Lorentz function.

In the silver halide grains used in the present invention, the above-mentioned low iodine layer and high iodine layer may or may not be clearly separated.

Even in the case of an emulsion in which two types of grains having different halogen compositions coexist and do not have a clear layered structure, two peaks appear in the X-ray diffraction.

Such emulsions cannot exhibit the excellent photographic performance obtained with the present invention.

In order to judge whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, the EPMA method (E
electron-Probe Micro AnaIy
This is possible by using the zer method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. XKS analysis using electron beam excitation allows elemental analysis of extremely small parts.

By this method, the halogen composition of each particle can be determined by determining the characteristic Xi intensity of silver and iodine emitted from each particle.

By confirming the halogen composition of at least 50 grains by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention.

In the emulsion of the present invention, it is preferable that the iodine content among the grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is 50% or less, further 35% or less,
In particular, it is preferably 20% or less.

Preferred halogen compositions of the silver halide grains of the present invention are as follows.

Part of the core (silver iodide mole fraction inside the grain is 10 to 40)
% iodobromide phase) is a high iodine silver halide with an average iodine content between 10 mol % and the solid solubility limit of 40 mol %. Preferably it is 15 to 40 mol%, more preferably 20 to 40 mol%. Depending on the method of preparing the core particles, the optimum value of the core iodine content may exist between 20 and 40 mol%, and in other cases between 30 and 40 mol%. Further, a portion of the core may further include a phase having a low iodine content.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

The average iodine content of the shell portion is lower than that of the core portion, preferably silver halide containing 10 mol% or less silver iodide, more preferably silver halide containing 5 mol% or less silver iodide. It is.

The distribution of silver iodide in the shell portion may be uniform or non-uniform.
The grains of the present invention have an average silver iodide content on the grain surface measured by the XPS method of 5 mol% or more, preferably 7 mol% or more and 15 mol% or less, and higher than the average silver iodide content of the shell portion. The distribution of silver iodide near the surface of the 0 grains may be uniform or non-uniform.

Silver halides other than silver iodide on the surface include silver chloride,
Either silver chlorobromide or silver bromide may be used, but a higher proportion of silver bromide is preferable.

Regarding the total halogen composition, the effect of the present invention is remarkable when the silver iodide content is 7 mol % or more.

More preferably, the total silver iodide content is 9 mol% or more, particularly preferably 12 mol% or more and 18 mol% or less.

The size of the silver halide grains of the present invention is not particularly limited, but is preferably 0.4 μm or more, more preferably 0.6 μm to 3.0 μm.
Preferably, the thickness is 5 μm.

Although it is possible for the emulsions of the present invention to have a wide grain size distribution, it is preferable to have an emulsion with a narrow grain size distribution.Especially in the case of normal crystal grains, the total weight or number of silver halide grains in each emulsion is A monodispersed emulsion in which the size of grains accounting for 90% of the average grain size is within ±40%, more preferably within ±30%, is preferred.

Even if the grains in the silver halide emulsion of the present invention do not contain twin planes, they may be normal crystals that do not contain twin planes. ,
For example, a single twin with one twin plane, two parallel twin planes
Depending on the purpose, it can be selected from among parallel multiple twins containing two or more nonparallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, and the like. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and the Tokko Kokko Sho 55-42.
737, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (
110) dodecahedral particles can be used. Furthermore, Journal of ImagingSci
ence Vol. 30, p. 247 As reported in 1986, a (hl) plane particle with (211) as a representative,
(hhl) plane particle represented by (331), (210)
(hko) plane grains represented by planes and (hkl) plane particles represented by (321) planes also require some ingenuity in their preparation methods, but they can be selected and used depending on the purpose. (100) plane and (
111) A tetradecahedral particle whose faces coexist in one particle, (1
Particles in which 00) and (110) planes coexist or (11
1) Particles in which two planes or many planes coexist, such as particles in which a plane and a (110) plane coexist, can also be selected and used depending on the purpose.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Phy
sique Photographique Paul
Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duff
+n+Photographic Es+ulsion
Chemistry (Focal Press+19
66), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (v, 1.Zelikmanet
Al, Making and Coating
Photographic Emulsion, 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 with the 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 good 0 grains are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which PAg 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 crystal shape and a nearly uniform grain size can be obtained.

In silver halide emulsions consisting of regular grains, grains of desired size are obtained by nucleation and grain growth using a double jet method while keeping PAg constant while maintaining a degree of supersaturation that does not cause re-nucleation. be able to.

Furthermore, the method described in Japanese Patent Application Laid-Open No. 54-48521 can be applied. In this method, in a preferred embodiment, a potassium iodobromide-gelatin aqueous solution and an ammonium silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide particles while changing the addition rate as a function of time. . At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate PH, PAg, temperature, etc. For more information, see Photographic Science and Engineering (Photograph).
ic 5science and engineering
g) Volume 6, pp. 159-165 (1962), Journal Op, Photographic Science (Journ
al orPhotographic 5science
), Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. 1,413
, No. 748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in the book by Creep [The Theory and Practice of Photography J (C1eve, Phot.

graphy theory and practice
(1930), p. 131; Gatoff, Photographic Science and Engineering (C
utoff, Photo-graphic 5cien
CE and Engineering), Volume 14,
pp. 248-257 (1970); U.S. Patent No. 4434
．． No. 226, No. 4,414,310, No. 4.433,
No. 048, No. 4,439,520 and British patent tube 2
It can be easily prepared by the method described in, for example, No. 112,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes.
It is detailed in No. 226.

Tabular grains are preferred as emulsions of the present invention.

In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
Tabular grains occupying the above amount are preferable.

In order to obtain monodisperse tabular grains, a fine grain tabular silver iodobromide emulsion can be obtained by adding equal amounts of an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide using a double jet method. can.

Subsequently, grain growth can be carried out in several batches or continuously by adding equal amounts of an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide, and increasing the total amount and rate of addition. The PAg being added is controlled to maintain a flat plate shape to the extent that no re-nucleation occurs, and pAg is preferably 9 to 7.

The crystal structure of these emulsion grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure.
No. 46, U.S. Patent No. 3,505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide.

Next, the preparation of silver halide grains having a silver iodide content of 5 mol % or more on the grain surface will be described.

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting soluble silver salt and soluble halogen salt can be selected from one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. As another type of simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (eg, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used.

When preparing the core, a halogenated primate solvent such as ammonia, rhodan salts, thioureas, thioethers, amines, etc. may be selected and used. An emulsion with a narrow particle size distribution of the core particles is desirable, especially the monodisperse core mentioned above. Whether the halogen composition of each grain is uniform at the core stage, which is preferably an emulsion, can be determined by the aforementioned X-ray diffraction method and EPMA method. When the halogen composition of the core particles is more uniform, the diffraction width of X-ray diffraction becomes narrower and sharper peaks are obtained.

Japanese Patent Publication No. 49-21657 discloses a method for preparing core particles with a uniform halogen composition among the particles. One is a double jet method in which 5 g of inert gelatin and 0.2 g of potassium bromide are mixed. A solution was prepared in 700 M of distilled water, stirred at 50°C, and aqueous solution 11 containing 52.7 g of potassium bromide and 24.5 g of potassium iodide and 100 g of silver nitrate were dissolved. 1ffi of the aqueous solution was simultaneously added at the same constant speed to the previously stirred solution over a period of about 80 minutes, and distilled water was added to bring the total amount to 31%, yielding silver iodobromide with a silver iodide content of 25 mol%. There is.

It has been determined by X-ray diffraction that the silver iodobromide grains have a relatively sharp iodine distribution. Another method is the rush addi-sin method, in which 33 g of inert bone gelatin, 5.4 g of potassium bromide, and 4.9 g of potassium iodide are mixed with 50 g of distilled water.
By stirring an aqueous solution of 0m at 70°C and instantly adding 125d of an aqueous solution containing 1112.5g of nitric acid, relatively uniform silver iodobromide particles with a silver iodide content of 40 mol% were obtained. is obtained.

JP-A-56-16124 has a halogen composition of 15 to 40.
It is disclosed that uniform silver iodobromide can be obtained by maintaining the PAg of a solution containing a protective colloid in the range of 1 to 8 in a silver iodobromide emulsion containing mol % of silver iodide.

After creating a silver iodobromide seed crystal containing a high concentration of silver iodide,
Irrigation can be achieved by increasing the addition rate over time, as disclosed by Irie and Suzuki in Japanese Patent Publication No. 4B-36890, or by increasing the concentration over time, as disclosed by Saito in U.S. Pat. No. 4,242,445. Uniform silver iodobromide can also be obtained by the method of growing silver bromide grains.

These methods give particularly favorable results. Irie et al.'s method involves the production of poorly soluble inorganic crystals for photography by a double decomposition reaction in which two or more inorganic salt aqueous solutions are simultaneously added in approximately equal amounts in the presence of a protective colloid. is added at a constant temperature acceleration or higher and at an addition rate Q (excluding constant temperature acceleration) that is lower than or equal to the addition rate proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, Qr or higher. and Q-αt2+βt+γ (α, β, T are constants determined by experiment, t is elapsed time) or less.

On the other hand, Saito's method is a silver halide crystal production method in which two or more inorganic salt aqueous solutions are simultaneously added in the presence of a protective colloid, and the concentration of the inorganic salt aqueous solution to be reacted is adjusted so that almost no new crystal nuclei are produced during the crystal growth period. This is to increase the amount to such an extent that it does not occur.

In addition, JP-A-60-138538, JP-A-61-
No. 88253, Japanese Unexamined Patent Publication No. 177535/1988,
JP-A-61-112142, JP-A-60-143
It can be prepared by applying the emulsion preparation method described in Japanese Patent No. 331 and the like.

There are many methods for introducing silver iodide into the shell portion of the silver halide grains of the present invention. When adding a water-soluble bromide salt aqueous solution and a water-soluble silver salt aqueous solution using a double jet method, the silver iodide in the core part may ooze out into the shell part. In this case, the PAg during addition may be adjusted and the silver halide solvent By using , the amount and distribution of silver iodide in the shell can be controlled. Also, an aqueous solution containing a mixture of water-soluble bromide and water-soluble iodide and a water-soluble root salt aqueous solution can be added by the double jet method, or a water-soluble bromide aqueous solution, a water-soluble iodide aqueous solution and a water-soluble silver salt can be added by the triple jet method. In order to introduce silver iodide to the 0 grain surface or 50 to 100 positions from the grain surface, add an aqueous solution containing water-soluble iodide after grain formation, or Fine silver iodide grains or fine silver halide grains having a high silver iodide content may be added.

In preparing the silver halide grains of the present invention, shelling may be carried out directly after core grain formation, but it is preferable to carry out shelling after washing the core emulsion with water for desalting.

Shell formation can also be prepared by various methods known in the field of silver halide photographic light-sensitive materials, but the simultaneous mixing method is preferable. Preferably, the required shell thickness varies depending on the particle size, but large particles of 1.0 g or more are covered with a shell thickness of 0.1 μm or more, and small particles of 1.0 μm or less are covered with a shell thickness of 0.05 μm or more. desirable.

The silver content ratio between the core part and the shell part is preferably in the range of 115 to 5, more preferably 115 to 3, and 1
A range of 15 to 2 is particularly preferred.

The silver halide emulsion used in the present invention is preferably a surface layer image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions as disclosed in JP-A-59-133542. can. Also, a light-white latent image type emulsion, which is covered with a thin shell, can be used depending on the purpose.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can also be used, and these ripening agents can be blended in their entire amount into the dispersion medium in the reactor before adding the silver and silver halide salts, or one or two ripening agents can be used. The above halide salts, silver salts, or peptizers can also be added and introduced into the reactor. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptohendithiazoles, mercaptohenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrohencitriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; There are many known antifoggants or stabilizers such as zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. Compounds can be added. For example, U.S. Patent 3,954
, No. 474, No. 3,982.947, Special Publication No. 1972-2
8.660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Representative examples are U.S. Pat. No. 2,688,545 and U.S. Pat.
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052, No. 3,527,641, No. 3,617
, No. 293, No. 3,628.964, No. 3,666.
No. 480, No. 3,672゜898, No. 3,679,4
No. 28, No. 3,703.377, No. 3,769,30
No. 1, No. 3 814.609, No. 3,837.862
No. 4.026,707, British Patent No. 1,344,2
No. 81, No. 1,507,803, Special Publication No. 434936
No. 53-12,375, JP-A-52-110,6
No. 18, No. 52-109,925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The dye may be added to the emulsion at any stage of emulsion preparation that has been known to be useful.
This is most commonly carried out after chemical sensitization is completed and before application, but chemical sensitization is performed as described in U.S. Pat. The spectral sensitization can be carried out at the same time as the chemical sensitization by adding it at the same time, or it can be carried out before the chemical sensitization as described in JP-A-58-113,928.
It is also possible to start spectral sensitization by adding it before the completion of silver halide grain precipitation. Furthermore, U.S. Patent No. 4,2
Adding these said compounds separately as taught in US Pat. is also possible, as described in U.S. Pat. No. 4,183,75
Any time during silver halide grain formation including the method taught in No. 6 may be used.

The amount added is 4X10-' to 8 per mole of silver halide.
X 10-'' moles can be used, but for a more preferred silver halide grain size of 0.2 to 1.2 μm, about 5X10-' to 2X10-S moles are more effective.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number and order of layers and non-photosensitive layers.A typical example is to use multiple silver halides with substantially the same color sensitivity but different light sensitivities on a support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of an emulsion layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 12751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (nL) / high sensitivity blue sensitive layer (r311) high sensitivity green sensitive layer (GJ() / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (RL), or B H / B L / G L / GH / RH / RL
or B H/B L/C; H/G L/RL
/RH, etc.

Furthermore, as described in Japanese Patent Publication No. 55-39492, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH may be arranged in this order from the farthest side from the support. can.

In addition, as described in Japanese Patent Publication No. 41-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, a medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

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

To improve color reproduction, U.S. Patent No. 4,663.2
No. 71, No. 4,705,744, No. 4.707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) N1117643
(December 1978), pp. 22-23, "1. Emulsion preparation and
dtVlles)”, and the same?4 [L18716
(November 1979), 64B pages, Graphic “Physics and Chemistry of Photography”, published by Paul Montell (P, Glaf
kidsChemie et Ph1sique
Photographique, Paul Monte
L, 1967), Duffin, "Photographic Emulsion Chemistry J,"
Published by Focal Press (G, F, Duffin,
Photo.

graphic emulsion chemist
y (Focal Press+ 1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikman et al., Ma
King and Coating Photo
graphic emulsion.

Focal Press+ 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Cutoff, Photographic Science and Engineering.
nce and Engineering), Vol. 14, p. 248A+257 (1970); U.S. Patent No. 4,4
34゜226, 4,414,310, 4.43
3.048, British Patent No. 4,439,520, and British Patent No. 2,112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure NQ1
7643 and Douma 18716, and the relevant parts are summarized in the table below.

In the present invention, it is preferable to use non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. They are fine silver halide grains that are not substantially developed and are preferably not coated with a coupler in advance.

The fine-grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and/or silver iodide as necessary, preferably silver iodide in a content of 0.5 to 100 mol%. It contains 10 mol%.

The fine grain silver halide has an average grain size (average diameter equivalent to a circle of projected area) of 0. O1 to 0.5 μm is preferable, and 0.
02 to 0.2 pm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

1 plate of additive layer uL7fiiL Tsuyoshi
Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers Pages 23-24 Page 648 Right column - Super sensitizers
Page 649, right column 4 Brightening agent
Page 24 5 Antifoggants Pages 24-25 and stabilizers 6 Light absorbers, filter dyes, UV absorbers 7 Antistain agents 8 Dye image stabilizers 9 Hardeners 10 Binders 11 Plasticizers, lubricants 12 pI! Fabric aids, surfactants 650 shells left to right column 649 pages right column to 650 pages left column 649 pages right column to 651 pages left column Same as above 650 pages right column 650 pages right column 25 pages right column 25 pages 26 pages 26 pages Page 27, pages 26-27, pages 25-26, 13 Static, page 27 Same as above. In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,987 and US Pat.
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Sou 17643, described in the patent described in ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401゜752, No. 4.
248,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1,425,020, British Patent No. 1.476.760, U.S. Patent No. 3973.968, British Patent No. 4.314.
No. 023, No. 4,511,649, European Patent No. 24
9°473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure Nα24220 (June 1984) ), JP-A-60-3
No. 3552, Research Disclosure Nα242
30 (June 1984), JP-A No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, US Patent No. 60-185951, US Patent No. 4.500.630, US Patent No. 4.540.654,
No. 4.556,630, International Publication WO3B1047
Particularly preferred are those described in Publication No. 95 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4052.212, U.S. Pat.
No. 4,296.200, No. 2,369,92
No. 9, No. 2.801.171, No. 2,772.1
No. 62, No. 2,895,826, No. 3,772,
No. 002, No. 3,758,308, No. 4,334
．． No. 011, No. 4.327,173, West German Patent Publication No. 3,329,729, European Patent No. 121 365A
No. 249.453A, U.S. Patent No. 3,446,
No. 622, No. 4,333゜999, No. 4,775
, No. 616, No. 4゜451.559, No. 4,42
7.767, 4.690.889, 4.2
No. 54,212, No. 4,296,199, Japanese Unexamined Patent Publication No. 6
Those described in No. 142658 and the like are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
4,367.282, 4.409,320, 4,576.910, British Patent 2,102,1
No. 37, European Patent No. 341.188A, etc.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3.234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163゜670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146,36
No. 8 is preferred, and also US Pat. No. 4,7
No. 74°181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in US Pat. No. 57-154234, US Pat. No. 60-184248, US Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds, or DIR redox-releasing redox compounds, couplers releasing dyes that recolor after separation as described in European Patent Nos. 173.302A and 313,308A, R,D, 11449, 2424
1. Bleach accelerator-releasing couplers described in JP-A No. 61-201247, ligand-releasing couplers described in U.S. Pat. U.S. Patent No. 4,
Examples include couplers that emit fluorescent dyes as described in No. 774,181.

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

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

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Esters of acids 11 ()
Riphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate),
Benzoic M ester W4 (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amide 1ll (N, N
-diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolid, etc.), alcohols or phenols (isostearyl alcohol,
2.4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters'R (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene,
diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat.
, No. 541, 230, etc.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or antifungal agents such as (4thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643, ゛ and turning magnet 18716
It is described from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate TI/f is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate TI/! can be measured according to techniques known in the art, e.g., by Green et al., Photographer, Sci, Eng.
It can be measured by using a swellometer (swelling membrane) of the type described in Vol.
I/A is defined as the time required to reach 1/2 of the saturated film thickness, with 90% of the maximum swollen film thickness reached when treated with a color developer for 13 minutes and 15 seconds at 30° C. as the saturated film thickness.

The membrane swelling rate TI/X can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%.

The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
ci17643, pages 28-29, and ci17643, 1B716
651, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also used as color developing agents, but p-phenylenediamine compounds are preferably used, and typical examples include 3-methyl-4-amino-N,N-diethylaniline, -Methyl-4-amino-N-ethyl-N-β
Hydroxyethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or P-1-luenesulfonates, etc. Can be mentioned. Among these, 3-methyl-4-amino-N-ethyl-N-β hydroxyethylaniline sulfate is particularly preferred.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH additives such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, hendithiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1, Representative examples include 1-diphosphonic acid, nitrilo-N,N,N-1-lyethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid) and their salts. This can be cited as an example.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virapritones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, the amount of -M to be refilled is 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 0d or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

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

That is, Volume of treatment liquid fi (cj) The above aperture ratio is preferably 0.1 or less, more preferably o,oot to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As bleaching agents, for example, metal compounds of polyvalent metals such as iron (Ill), peroxides, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediamine. Aminopolycarboxylic acids such as tetraacetic acid, diethylenetriaminepentaacetic acid, cyclohedondiaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. Among these, aminopolycarboxylic acid iron (III) complex salts, including ethylenediaminetetraacetate iron (I [[Hfi salt) and l,3-diaminopropane tetraacetate iron (III) complex salt, It is preferable from the viewpoint of processing and prevention of environmental pollution.Furthermore, aminopolycarboxylic acid iron ([[l) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions.These aminopolycarboxylic acid iron (ffl) complex salts are pH of the bleach solution or bleach-fix solution used
is usually 4.0 to 8, but it is also possible to process at an even lower pH for speeding up the process.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059°988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 5395631, No. 53-104232, No. 53-124424, No. 53-141623,
No. 53-28426, Research Disclosure N
Compounds having a mercapto group or a disulfide group described in No. a17129 (July 1978), etc.;
Thiazolidine derivatives described in No. 0-140129; Japanese Patent Publication Nos. 45-8506, 20832-1983, 5
No. 3-32735, thiourea derivatives described in U.S. Pat. No. 3,706.561; West German Patent No. 1.127.715
Iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966.410 and 2.748.430; Japanese Patent Publication No. 45-88
Polyamine compound described in No. 36; other JP-A-49-49
No. 0.943, No. 49-59゜644, No. 53-94
, No. 927, No. 54-35.727, No. 55-26,
Compounds described in No. 506 and No. 58163.940; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
Preferred are the compounds described in U.S. Pat.
, 552,834 are also preferred. These bleach accelerators may be added to the light-sensitive material, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pka) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. Preservatives for fixers and bleach-fix solutions are preferably sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294769A. For the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids. The total time for the desilvering process is
It is preferable that the length be as short as possible so long as desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes.

In addition, the treatment temperature is 25°C to 50°C, preferably 35°C.
°C to 45°C. In the preferred temperature range,
The desilvering speed is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a forwarding means can significantly reduce the carry-over of processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of the 5ociety
of Motion Picture and
It can be determined by the method described in Te1evision Engineers, Vol. 64, P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be effectively used. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technical information [Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Industrial Technology Association, Japan Antibacterial and Antifungal Science Kinpei “Encyclopedia of Antibacterial and Antifungal Agents J”
(1986) may also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
All known methods described in No. 4 and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various types of beef shavings and antifungal agents to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Virazolids may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 A silver iodobromide tabular emulsion was prepared by the method described in JP-A-62-209445. An aqueous solution of 25 g of inert gelatin, 6 g of potassium bromide, and 11 + fJ of distilled water was stirred at 60°C, and then an aqueous solution of 35 g of silver nitrate dissolved therein was stirred at 60°C.
cc and potassium bromide 3.2g, potassium iodide 0.9
After adding 35 cc of an aqueous solution in which 8 g of PAg was dissolved at a flow rate of 70 cc/min for 30 seconds, the PAg was increased to 10 and 3
A seed emulsion was prepared by aging for 0 minutes.

Subsequently, a predetermined amount of the aqueous solution 12 in which 145 g of silver nitrate was dissolved and an aqueous solution of a mixture of potassium bromide and potassium iodide were added in equimolar amounts at a predetermined temperature and a predetermined PAg at an addition rate close to the critical growth rate. A core emulsion was prepared.

Subsequently, equimolar amounts of the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in preparing the core emulsion were added at a rate close to the critical growth rate to coat the core. A core/shell type silver iodobromide tabular emulsion was prepared. Let this emulsion be A, and on the other hand,
An emulsion in which grains were formed by adding a silver oxidizing agent in the amount shown in Table 1-1 one minute before the start of shell formation was designated as BE.

Compound 1- listed in Table A as thiosulfonic acid
Emulsions F and G were prepared by using Emulsion No. 2, but with the addition timing at the end of redispersion.

These emulsions A to G all have an equivalent sphere diameter of 1°4 μm1
The iodine content in the core was 125 mol%, the iodine content in the shell was 3 mol% (core/shell ratio 1/1), the average iodine content was 14 mol%, and the surface iodine content by XPS was 5.5 mol%.

These emulsions A-G are then optimally chemically sensitized using chloroauric acid and sodium thiosulfate, but either prior to or at the end of this chemical sensitization, the chemical sensitization shown in Table 1-1 is carried out. Table 1-1 summarizes the emulsions prepared by JJL to which potassium thiocyanate was added.

-I -2 -I -2 -3 -I -2 -I -2 -I -2 -I -1 -2 -6 5X10-" mol Immediately before the start of chemical sensitization 3 xto-'tm Particle formation period 5X10-' Immediately before the start of chemical sensitization At the end of chemical sensitization 5XIO-' Immediately before the start of chemical sensitization 6 The symbols other than 0□ indicate the symbols of the compounds shown in Table A.

The emulsion and protective layer were coated on a triacetyl cellulose film support provided with an undercoat layer in the coating amounts shown in Table 1-2.

Table 1-2 +11 Emulsion layer 0 emulsion... Emulsion shown in Table 1-1 (silver 1.7 x 10-" mol/I) O coupler (1,5 x 10" 3 mol/-) O tricresyl phosphate (1 , log/nf) 0 gelatin (2,30 g/ffr) (2) Protective layer 02.4-dichlorotriazine-6-hydroxy-S-
Triazine sodium salt (0.08 g//) 0 Gelatin (1.80 g/rrr)
After 2 months, exposure for sensitometry was applied, and the next color development process was performed.

The concentration of the treated sample was measured using a green filter.

The results of the photographic performance obtained are shown in Table 1-3.

The development process used here was carried out at 38°C under the following conditions.

1. Color development... 2 minutes 45 seconds 2. Drifting
White... 6 minutes 30 seconds 3, wash with water...
... 3 minutes 15 seconds 4, fixation ... 6 minutes 30 seconds 5, washing ... 3 minutes 15 seconds 6, stability ... 3 minutes 15 seconds each The composition of the treatment liquid used in the process is as follows.

Color developer Sodium nitrilotriacetate 1.48 Sodium sulfite Sodium carbonate Potassium bromide Hydroxylamine sulfate 4-(N-ethyl-N-βhydroxyethylamino)-2-Methyl-aniline sulfate Add aqueous solution to bleach solution bromide Ammonium Aqueous ammonia (28%) Ethylenediamine-sodium tetraacetate Add glacial acetic acid water to fix fixing solution Sodium tetrapolyphosphate Sodium sulfite Ammonium thiosulfate 700 g/j 4,5 g 1 160.0 g 25.0 d 30 g 4- 1 2,0 g 4.0g 175.0m Sodium bisulfite Add 4.6g water 11 Stabilizing liquid formalin 8. Add water 11 Exposure is 1/100
A conventional wedge exposure was performed in seconds.

The light source used was one whose color temperature was adjusted to 4800"K using a filter, and a blue filter (BPN42 manufactured by Fuji Photo Film) was used to extract blue light. Sensitivity varies from fog to optical density. Comparisons were made on the basis of a score of 0.2.Sensitivity was expressed as relative sensitivity, with the sensitivity of the sample using emulsion A-1 set as 100.

Table 1-3 1 (Comparison) A-1 2 (Same as above) A-2 3 (Same as above) B-1 4 (Present invention) B-2 5 (Comparison) B-3 6 (Comparison) C -1 7 (present invention) C-2 8 (comparison) D-1 9 (present invention) D-2 10 (comparison) E-1 11 (present invention) E-2 12 (comparison) F-1 13 (same as above) G-1 10095 11792 8485 LL! 1L LU 90 88 80 81 1 Earthwork Earth 1 75 75 Upper 11115- 80 8〇1■''-- Mouth J- 110100 10490 0,22 0,24 0,19 1 Strand 0.22 0.19 0.22 0.19 0.2 Yu 0.25 Vertical 1st 0.18 0.20 0.21 0.36 0.18 0.2 above 0.20 0.19 0.22 0.17 11 0.28 0133 0 .30 0, Ol +0.12 0, Ol +0.01 +0.02 0.00 0.00 -0.02 0.00 +0.03 +0.01 +o, is +0.10 *) 25℃60%RH12 months As is clear from Table 1-3 showing the results after aging, it can be seen that the emulsion of the present invention has suppressed capri and has high sensitivity.

Furthermore, it can be seen that the samples of the present invention exhibit excellent storage stability with little decrease in sensitivity and small increase in capri over time.

Example 2 In the preparation of emulsion B-2 in Example I, emulsions prepared using ammonium thiocyanate or potassium selenocyanate instead of potassium thiocyanate were
-4 and B-5.

Emulsions B4 and B-5 were coated according to the method described in Example 1.

These samples were evaluated in the same manner as in Example 1, and the results shown in Table 2 were obtained.

As is clear from Table 2, the emulsions of the present invention have suppressed capri, high sensitivity, and excellent storage stability.

Example 3 By changing the mixing ratio of potassium bromide and potassium iodide during grain formation of emulsions A and B described in Example 1, emulsion H
-K was prepared. These emulsions have an equivalent sphere diameter of 1.4 μm.
, the core/shell ratio was 1/l. Table 3 shows the iodine content of the core and shell, the average iodine content, and the surface iodine content determined by XPS.

Emulsions H and I were optimally chemically sensitized using chloroauric acid and sodium thiosulfate under conditions as shown in Table 3.

These emulsions were coated according to the method described in Example 1.

These samples were evaluated in the same manner as in Example 1, and the results shown in Table 3 were obtained.

From Table 3, the effect of the present invention is that the surface iodine content is 5 mol%.
It can be seen that this is particularly noticeable in emulsions containing 7 mol % or more.

Example 4 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution over 100 minutes at 75° C. with vigorous stirring to obtain a silver bromide emulsion having an average particle size of 1.3 μm. Further, the shell was treated for 40 minutes in the same precipitation environment as the first time, and a silver bromide emulsion having a final average grain size of 1.5 μm was prepared.

On the other hand, one minute before the start of shell formation, 3.times.10@-' moles of Compound 1-6 listed in Table A were added per mole of silver, and the emulsion in which grains were formed was designated as M.

Emulsions N to S were prepared in the same manner as Emulsions N and M except that 1.8, 2.3 and 3.5 mol % of potassium iodide were present during precipitation. The ill-produced emulsions are summarized in Table 4.

Emulsions J-Q were optimally chemically sensitized using chloroauric acid and sodium thiosulfate under the conditions shown in Table 4.

These emulsions were coated according to the method described in Example 1, and the samples were evaluated and the results shown in Table 4 were obtained.

Table 4-2 shows that the effect of the present invention is remarkable when the iodine content is 2% or more, particularly 3% or more.

Example 5 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is g/g for silver halide and colloidal silver.
The amounts of silver are expressed in rd units, and the amounts of coupler additives and gelatin are expressed in g/rd units, and the sensitizing dyes are expressed in moles per mole of silver halide in the same layer. .

1st layer: Antihalation layer black colloidal silver Silver coating amount 0.2 Gelatin V-1 V-2 Cpd-1 Cpd-2 olv-1 olv-2 2nd layer: Intermediate layer fine grain silver iodobromide (Ag1 1. 0 mol% sphere equivalent diameter 0.0
7μm) 2.2 0.1 0.2 0, 04 0, 02 0, 30 0.01 Silver coating amount 0.15 Gelatin 1. 0ExC
-40,03 Cpd-3Q・2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21 %, tabular grain, diameter/thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) coated with silver! 0.40 1, 0 4.5X10-'mol 1.5X1 (I'mol 0.4X10-'mol 0.50 0.11 0.009 0.023 0.24 Gelatin ExS-1 ExS-2 ExS-3 xC-1 xC-2 xC-3 xC-4 Solv-1 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag 18.5 mol%, internal high AgT type, equivalent sphere diameter 1.0 μm, sphere Coefficient of variation of equivalent diameter 25%, plate-like particles, diameter/thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.7 ExS-1 ExS-2 ExS-30°xC-1 xC-2 xC-4 Solv 1 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion ■ Coefficient of variation of equivalent sphere diameter 28%, diameter/thickness ratio 6.0) 3X10-'mol lXl0-'mol3X10-'mol0, l0 0,05 0.025 0,10 Platy particles, gelatin ExS-I ExS-2 ExS-3 xC-2 ExC~4 xC-5 Solv-1 Silver coating amount 1.50 0, 6 2X10-'mol 0. 6X10-'mol 0.2X10-'mol 0.08 0.01 0.06 0.12 Solv-20,12 6th layer: Intermediate layer gelatin 1.0Cpd
-40,l 5olv-10,1 7th N: First green-sensitive emulsion layer Silver iodobromide emulsion (Ag [5.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter/thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, variation in equivalent sphere diameter Coefficient 18%, dodecahedral particles) Silver coating amount 0.16 Gelatin 1.2ExS-
55xlO-'mol ExS-62xlO-'mol ExS-71xlO-'mol ExM-10,50 xM-2 xM-5 Solv-1 o1v-4 8th layer; .5 mol%, internally high iodine type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 3.0) 0, 10 0, 03 0.2 0, 03 Gelatin ExS-5 ExS-6 ExS-7 xM-I xM-2 xM-3 Solv-I 0IV-4 9th layer: Intermediate layer silver coating amount 0.57 0.35 3゜5X10-'Mole 1.4X10- 'Mole 0.7X10-'Mole 0.12 0.0I O2O3 0.15 0.03 Gelatin 0.5Solv
-10,02 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion■ Silver coating amount 1.3 Gelatin 0.8ExS-
52X10-'mol ExS-60,5xto-'mol ExS-70,5xto-'mol ExM-40,04 ExC-40,005 ExM-60,01 Cpd-50,01 Solv-10,2 11th layer: Yellow Filter layer cpd-6o, 05 gelatin 0. 5Sol
v-10,1 12th layer: Intermediate layer gelatin 0.5Cpd
-30,1 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (Ag1 2 mol%, uniformly iodine type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter/ Thickness ratio 7.0) Silver coating amount 0. 2 Gelatin 1. 0ExS
-83xlO-'mol ExY-10,6 ExY-20,02 Solv-10,15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 1'9.0 mol%, internal height A
GL type, equivalent sphere diameter 1.0μm, coefficient of variation of equivalent sphere diameter 16
%, octahedral particles) Silver coating amount 0.19 Gelatin 0.3ExS-
82X10-'mol EXY-10,22 Solv-10,07 151: Intermediate layer fine grain silver chloride exposure 12 mol%, uniform iodine type, equivalent sphere diameter 0.13 μm) Silver coating amount
0.2 Gelatin 0.36 No. 16N
: Third blue-sensitive emulsion layer × 101 mol silver iodobromide emulsion m Silver coating amount 1.55 Gelatin 0.5ExS-
91,5xxo-'mol xY-1 0,2 Solv-1 17th N: First protective layer gelatin V-1 V-2 Solv-1 Solv-2 0,07 1,8 0,1 0,2 0,0I O3Ol Fine particle silver chloride (equivalent sphere diameter 0.07 μm) Silver coating amount 0
．． 36 Gelatin 0.7 Polymethyl methacrylate particles (1.5 μm in diameter) 0.2W-1
0,02 H-10,4 Cpd-71・0 In addition to the above, each layer contains B-1 (total 0.20 g/r+()
, 1,2-benzisothiazolin-3-one (about 200 ppm on average relative to gelatin), n-butyl, p-hydroxybenzoate (about 1.000 ppm), and 2-phenoxyethanol (about 10,000 ppm relative to gelatin).
) was added.

LIV-1: CH3CH3 (CHz -C-h(C11! -C-斤Co
C00CH3 18th layer: 2nd protective layer x/y=7/3 (weight ratio) UV 2 : xC H xC 0■ (n) C+Jis xC xM-1 xC-3 xC H xM-2 xM-3 CH.

Shil ExM-4 Shi! ExM-5 xY-2 pd pd-2 Shi1i Fl14UI+ ExM ClO2 XY-1 pd-3 H pd CJ+i pd H Cpd-6 Cpd-7 -1 xS-3 xS-5 F, xS H3 ■ C) Ix= CHSOzCHxCONH-CHtCH8・
cnsotcooC0NH-CH! Φ −1 xS−1 xS−2 xS−7 xS−9 !
It was also used as silver iodobromide emulsion (1) in the 10th layer. Also,
By appropriately changing the iodine content and the silver content in the shell part during the formation of the core grains of Emulsion A-1, the iodine content of the core with an equivalent sphere diameter of 1.7 μm was 42 mol%, the iodine content of the shell was 3 mol%, and the average iodine content was 14. An emulsion was prepared with a surface iodine content of 7.0 mol % as determined by XPS. This emulsion was optimally chemically sensitized with sodium thiosulfate and chloroauric acid and was used as the silver iodobromide emulsion (2) in the 16th layer.

Emulsions A-2, B-1, B-2, and D-2 described in Example 1 were used instead of Emulsion A-1 described in Example 1.
Samples 102 to 107 were prepared in the same manner as sample 101 except that emulsion B-4 described in Example 2 and E-2 were replaced.

These samples were tested immediately after application and at a temperature of 40°C and a humidity of 60%.
After one month, exposure for sensitometry was applied under this environment, and the following color development process was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. The results are summarized in Table 5.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water wash 3 minutes 15 seconds Stable 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene 1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g Potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino) 2-methylaniline sulfate Add aqueous solution H Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Add water and al Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 1, 3gg 2, 4g 4, 5g 1, θ1 10, 0 100.0g 10.0g 150.0g 10.0g 1, 01 6 .0 1.0g 4.0g Ammonium 1000sulfate aqueous solution (70%) 175. (Add 4.6 g of ld sodium bisulfite water
1.01 pH 6.6 Stabilizing liquid formalin (40%) 2. (Add 0.3 g of ld polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 1.01 Table 5 shows that the effects of the present invention are also expressed in multilayer color photosensitive materials. .

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Claims (4)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer is formed into grains in the presence of at least one oxidizing agent for silver; A silver halide photographic material comprising a silver halide emulsion chemically sensitized in the presence of at least one of thiocyanate and selenocyanate. (2) The silver halide photographic material according to claim (1), wherein the oxidizing agent for silver is at least one compound represented by any one of formulas (I) to (III). (I) R-SO_2S-M (II) R-SO_2S-R^1 (III) R-SO_2S-L_m-SSO_2-R^2
In the formula, R, R^1, R^2 may be the same or different,
It represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of general formulas (I) to (III) may be polymers containing divalent groups derived from the structures shown by (I) to (III) as repeating units. Also,
When possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (3) Claim (1) or (2) which is a silver halide emulsion comprising silver halide grains having a silver iodide content of 1 mol% or more and a silver bromide content of 50 mol% or more. ).The silver halide photographic material described in ). (4) The silver halide photographic light-sensitive material according to claim (3), which is a silver halide grain having a silver iodide content on the surface of the grain of 5 mol % or more.