JPH01102548A - Photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a silver halide emulsion which has excellent sharpness and is improved in pressure characteristic by having a high-iodine layer in a core and having a silver halochloride which is partially counted to halogen, silver thiocyanate or silver citrate in the particle. CONSTITUTION:The core part of the particle is formed of silver halide contg. 10-45mol% silver iodide and the silver salt having the solubility higher than the solubility of silver bromide is deposited during the course of particle forma tion after the core formation. Silver halochloride, silver thiocyanate or silver citrate are exemplified as the silver salt having the high solubility. The silver halide is deposited and is converted to the halogen while the shell part is formed by addition of an aq. silver nitrate soln. and aq. halide compd. further onto the silver salt having the solubility higher than the solubility of the silver bro mide. The silver halide particle of the core/shell type having the silver halochloride which is partially converted to halogen, silver thiocyanate or silver citrate in the particle is thus obtd. The emulsion which has the high sharpness and is improved in pressure characteristic is thereby obtd.

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to a silver halide photographic emulsion. It has a high iodine layer in the core, a partially halogen-converted silver octachloride layer inside the grains, and a thiocyanate. This invention relates to a core/shell type silver halide photographic emulsion having a silver layer or a silver citrate layer. (Prior Art) Generally, a silver halide emulsion is applied to a photographic material coated with various pressures. , General photographic negative film is folded or pulled when it is rolled up into a cartridge or loaded into a camera, or pulled for frame advance. Sheet films, such as wood, are handled directly by hand, so
Breaks and bends occur frequently. Furthermore, all types of sensitive materials are subjected to great pressure during cutting and processing. In this way, various pressures are applied to the photographic material (pressure is applied to the silver halide grains through the medium of gelatin, which is a binder for the silver halide grains, and the plastic film that is the support). It is known that when pressure is applied to silver halide grains, changes occur in the photographic properties of photographic materials.For example, K*
B-Mather%J-09t*8
o C@人m1jr, 10j4C (/Per), P, F
aelensand, P, do 8met, 8
ci, et Ind, Phot,. 21, Aj, /71 (/ 5F7riP, Faelens
. This is reported in detail in J, Phot, 8ci, J, 101 (/ri!), etc. Next, we need to provide photographic materials whose photographic properties are not affected in any way by these pressures. There is a strong desire to improve the pressure properties by adding plasticizers such as polymers and emulsions, and by reducing the silver halide/gelatin ratio in silver emulsions. For example, in British Patent No. 711.≦lr, a heterocyclic compound is used in British Patent No. 711.≦37 (in which an alkyl phthalate is used, The number is alkyl ester, US Patent 1
lIi co, No. 240, 44041 contains polyhydric alcohol, same! , /co/, No. 040 describes a method using cellulose in carboxyl, JP-A No. 1017 uses paraffin and Cald:yrR salt, and JP-A No. 13-2 Rort uses alkyl acrylate and an organic acid. is disclosed. However, the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, so there is a limit to its usage. The method is also difficult to achieve sufficient effect. On the other hand, in recent years, silver halide photosensitive materials have become more sensitive and smaller in format, and there is a strong desire for photosensitive materials with even higher sensitivity and superior image quality. In response to these demands, JP-A-Shobu 0-/1fiJJJ/ has a clear double structure and a highly iodine core, resulting in high sensitivity, less scratching, and excellent graininess. It has been shown that silver halide emulsions can be produced. It is also known that dye adsorption is enhanced by highly iodinated surfaces1) (T, H, James TheT
theory of the photograp
hicProcess P, 24A/ ) It is convenient for color sensitization. Ninth, surface-high iodine emulsions have a large edge effect and are effective for producing photographic materials with excellent sharpness. However, these highly iodinated emulsions often exhibit pressure fogging and pressure sensitization, and countermeasures are required. US Patent Co! Ri J co! No. 0 discloses emulsion grains in which silver chloride emulsion grains have been subjected to nitrogen conversion with bromide ions or iodide ions. Japanese Patent Publication No. 16971/1983 discloses a method of using a hardened emulsion by chemically sensitizing the surface of the emulsion. Japanese Unexamined Patent Application Publication No. 2003-120002 discloses an emulsion in which an emulsion containing chloride ions is subjected to halogen conversion using bromide ions or iodide ions in the presence of a solvent. Japanese Patent Application Laid-Open No. 77-77 discloses that silver halide grains are grown by adding bromide ions or iodide ions to a silver chloride emulsion within 10 minutes after grain formation for physical ripening. A method is disclosed. "However, this method of preparing emulsion grains does not allow control of grain formation, and as described in the patent, the halogen conversion results in completely different grain sizes and shapes. Japanese Patent Publication No. 4/-J/≠1≠ discloses a method of depositing silver bromide on silver chloride grains in a layered type rather than a halogen conversion type. US Pat. No. 4C Tata! No. 177 discloses discloses a silver halide emulsion having a silver chloride layer in one layer of the inner core of the silver halide grains.The tabular grains thus obtained have a silver chloride layer as described in the specification. Although properties inherently possessed by silver chloride i, such as rapid development characteristics, can be obtained, properties originally possessed by silver iodobromide, such as improved sensitivity/graininess relationship, are lost. Silver halide grains containing iodide ions are disclosed. U.S. Pat. !Tatatada No. 3J discloses that the pressure characteristics are improved by providing a high iodide layer inside the tabular grains. JP-A-Sho ≦/-/1
No. 3 discloses that pressure is improved by having a higher iocide content in the central region of the tabular grains than in the outer regions. However, like this
The method using a chemical compound not only improves the pressure characteristics but also has a significant effect on photographic properties such as developability, and there are limitations to its use. (Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide emulsion with high sensitivity, excellent graininess and sharpness, and improved pressure characteristics. (Means for solving the problems) The above object of the present invention was achieved by the following means. That is, in a silver halide photographic emulsion consisting of silver halide grains having a core/shell structure, the core portion of the grain is made of silver halide containing 10 to 1% silver iodide, and the inside of the grain is A silver halide photographic emulsion characterized by having a partially halogen-converted silver halochloride layer, a silver thiocyanate layer, and a silver citrate layer, in particular, a silver iodide content on the surface of the emulsion grains is j m
o This was achieved by a silver halide photographic emulsion characterized by an I- or higher. In the present invention, the core part in the core/shell type silver halide grains refers to the silver halide layer located inside the partially halogen-converted layer, and the shell part refers to the partially halogen-converted layer. This refers to the silver halide layer located on the outer side of the silver halide layer. In the present invention, the “surface” of the particle refers to E8CA (XPS
depth (approximately j-o from the surface)
A). The deposition of a highly soluble silver salt and the halogen conversion in the present invention can be carried out by the following method. After core formation, a silver salt having higher solubility than silver bromide is deposited during grain formation. The base grains on which silver salts having higher solubility than silver bromide are to be deposited account for 3% or more and less than 1% of the final grain volume. Preferably, it occupies an area of 10 arcs or more and 0 arcs or less, and more preferably 10 arcs or more and 10 arcs or less. Only when these various conditions are satisfied can changes in particle size and shape during the subsequent halogen conversion process be minimized. Deposition of highly soluble silver salts is made possible by consuming excess bromide ions by adding an aqueous silver nitrate solution. Alternatively, this can be achieved by adding an emulsion of highly soluble silver salt and ripening. The solubility of such silver salts in water is higher than that of silver bromide, and the solubility of ao@c in water is 0.
001, preferably 0.000. Useful silver salts with greater solubility than silver bromide include silver octochloride, silver thiocyanate, and silver citrate. Examples of the octoday silver chloride include silver chloride and silver chlorobromide, silver chloroiodobromide, or silver chloroiodide containing silver chloride and silver chloride f:lO molar width or more. In the present invention, preferably norosilver chloride and thiocyanate, more preferably octoday silver chloride are effective. In particular, silver chloride, silver chlorobromide, and silver chloroiodobromide with a silver chloride content of 40% or more are effective, and among them, silver chloride is effective. The amount of these silver salts deposited depends on the underlying particles.

[Core part] More than 1 mole of silver. less than 1 molar width, preferably more than 1 molar width and less than 70 molar width,
More preferably 40 moles or less, most preferably 1 to 40 moles
4LO mol%. Only when these conditions are satisfied can changes in particle size and shape during the subsequent halogen conversion process be reduced. Subsequently, halogen conversion is carried out. The halogen conversion is carried out by adding an aqueous halide solution and an aqueous silver nitrate solution, or by adding only an aqueous halide solution. That is, in order to convert a silver salt having higher solubility than silver bromide into a halogen by adding an aqueous halide solution, potassium bromide,
Preferably this is done by adding potassium iodide or a mixture thereof. At this time, an appropriate amount of sodium chloride may be included in the halide aqueous solution. On the other hand, in order to further deposit silver halide on a silver salt having higher solubility than silver bromide to form a shell part and perform halogen conversion, the silver halide to be deposited may be silver bromide, silver iodide or Silver iodobromide is preferred. The silver halide deposited at this time may contain an appropriate amount of silver chloride. The deposition conditions vary depending on the temperature, deposition rate, and halogen composition of the deposited silver halide! At 00C, pAg
7.7 or more, preferably r, o or more, more preferably r
, 7 or more, and in 7j@C, the pA is 17 or more, preferably 7.7 or more, more preferably t, o or more. At temperatures between to''c and yz @C, this pA
The deposition rate is preferably below the critical growth rate, and particularly preferably below the critical growth rate. As a method for depositing silver halide, it is preferable to add an aqueous silver nitrate solution and an aqueous halide solution, or to add fine particles of silver halide. The silver nitrate aqueous solution may be added after or simultaneously with the addition of the halide aqueous solution. ζThe halogen conversion here does not mean that all silver salts that are more soluble than silver bromide are substantially replaced by silver bromide. Preferably more than 10 moles, more preferably more than 30 moles, even more preferably! It is preferable that more than 0 moles of silver bromide are replaced by Kf. The degree of this halogen conversion can be easily calculated by analyzing the amount of deposited silver salt having higher solubility than silver bromide and the content of highly soluble silver salt after halogen conversion. X-ray diffraction, BPMA (a method of scanning silver halide grains with an electron beam and detecting the silver halide composition), EaCA method (a method of irradiating X-rays and spectroscopy of photoelectrons emitted from the grain surface), etc. This can be confirmed by combining them. In the present invention, this is achieved by further precipitating silver salt and growing grains after undergoing halogen conversion. (Formation of shell portion) This grain growth is carried out by adding silver ions and bromide, iodide, and chloride ions to the reaction vessel using well-known techniques. The halogen composition of the shell portion after halogen conversion may be uniform or may have a layered structure. When the layered structure t'' is present, the grain surface contains silver iodide in an amount of 3 mol% or more, preferably 1 mol or more, and furthermore, the inner layer of the silver iodide pulp layer has the silver iodide content as described above. It is desirable that the grain density be lower than that of the grains.In addition, iodide may be added to the surface after grain formation to make the surface highly iodinated. By highly iodinating the grain surface, sharpness is high and pressure resistance is improved. An improved emulsion can be obtained.The silver halide in the shell part deposited after halogen conversion is 10A-20 molar of the entire grain and 30 molar of the bone.
The width is preferably 70 to 70 molar. High iodine silver halide is present in the core portion of the silver halide grains in the present invention, and the iodine content ranges from more than 10 moles! Between the molar widths. Preferably it's from /j mole attack to 30 mole whisper. The core portion may consist of a homogeneous phase of silver iodobromide or silver chloroiodobromide with an iodine content of 10 NIA 1 mole, or may have an iodine content of 1 mole.
A layer having a different halogen composition may be present inside or outside the silver iodobromide or silver chloroiodobromide of oNaz mole. For example, if the sodium carbonate content is 10% of the silver iodobromide of 10 mols of NaZ
There may also be an outer layer having a silver bromide or iodine content of less than IO%. The proportion of high iodo silver halide in the core is preferably from O to iOO molar. For preparing the core particles, methods such as an acidic method, a neutral method, and an ammonia method can be selected, and a method for reacting a soluble silver salt and a soluble halogen salt can be selected from a one-sided mixing method, a simultaneous mixing method, a combination thereof, and the like. As one form of the simultaneous mixing method, a method in which DAg 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, ammonia, Rodin, thioureas, thioethers,
Any silver halide solvent such as amines may be used. The silver halide grains of the present invention may be normal crystals such as 4#'i, cubic, octahedral, dodecahedral, or tetradecahedral, or may be twin crystal grains such as spherical, potato-shaped, or tabular. The size of the emulsion grains which have been partially halogen-converted inside the grains of the present invention is not particularly limited, but is preferably 1-μm or more. Ninth, even more favorable results may be obtained by using monodisperse particles. The silver halide emulsion of the present invention contains a cadmium salt, a zinc salt, a talicum salt, an iridium salt, or a complex salt thereof, or a rhodium salt, in the process of grain formation or physical ripening. They may coexist. The silver halide emulsion of the present invention is usually spectrally sensitized, but
Preferably, it is used after being spectrally sensitized. Methine dyes are usually used as the spectral sensitizing dyes used in the present invention, and these include cyanine dyes, merocyania dyes, complex sialan dyes, complex merocyania dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Dyes are included. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is,
vilorin nucleus, ochinacillin nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these −; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindo V Nin nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus,
Benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms. IcI'/7E7 dye or complex merocyania dye contains pyrazoline-! as a core having a ketomethylene structure. −
On nucleus, thiohydantoin nucleus, corchio Φsaciridin-2. A 7- to 4-membered heterocyclic nucleus such as a thiazolidine-dione nucleus, a thiazolidine-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied. Among the above dyes, particularly useful sensitizing dyes for the present invention are cyanine dyes. Specific examples of cyanine dyes useful in the present invention include dyes represented by the following general formula CI). General formula (1) In the formula, 2□ and z2 represent a heterocyclic nucleus used in cyanine dyes, particularly a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus, a natuthiazole nucleus, an oxazole nucleus, an odoroshirin nucleus, a benzoxazole nucleus, Complete naphthoxazole nucleus, tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidacilline nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, or indolenine nucleus, etc. The atomic group f required for
Alkoxy group, carzexyl group, alkoxycarbonyl group, alkyl sulfamoyl group, alkyl group Iζ
It may be substituted with a moyl group, an acetyl group, an acetyl group, a cyano group, a tricumylomethyl group, a trifluoromethyl group, a nitro group, or the like. Ll or li represents a methane group or a substituted methine group. Examples of the substituted methine group include a lower alkyl group such as a methyl group and an ethyl group, a phenyl li% 11-substituted 7-enyl group, a methoxy group, and a methine group substituted with a methoxy group. B, and R2 are an alkyl group having a carbon number of /Nj; a substituted alkyl group having a sil group in the caldi group; a β-sulfoethyl group, r
-sulfopropyl group, δ-sulfobutyl group, -1 (J-
Substituted alkyl groups having a sulfo group such as a sulfopropoxy)ethyl group, a J-(J-(J-sulfopropoxy)ethoxy)ethyl group, and a 2-hydroxy sulfopropyl group;
t-Represents an allyl group and other substituted alkyl groups commonly used as N-substituents of cyanine dyes. mo represents 3'fr, and X1e represents an acid anion group commonly used in cyanine dyes, such as an iodine ion, a bromide ion, a p-toluenesulfonic acid ion, or a perchlorate ion. No represents 1 or 1t-, and when a betaine structure is formed, n□ is 1. Representative compounds of spectral sensitizing dyes that are effective when used in the present invention are shown below. ■7/ ■-1 -j Io-dar-r -2 80 K 803- 1-/ / 803K 803"- 1-/Ko-1803"" 1-/ J l-/ 4L I-/ j Sensitizing dye is added after the chemical ripening, and the sensitizing dye is added before the chemical ripening.For the silver halide grains of the present invention, the sensitizing dye is most preferably added during the chemical ripening or before the chemical ripening (for example, during grain formation, during physical ripening). ) The silver halide emulsion is usually chemically sensitized.The most preferred embodiment of the emulsion of the present invention is to chemically sensitize it so that it is used as a negative-working silver halide emulsion. For chemical sensitization, for example H, Fr1eser
), ed.DieGrundligen der Pho
togrmphlschenProzesse mHS
Eyeberhal ogenlden) (akademitsushie ferluxguzelshacht lribu r)bu 7! ~7J
The method described on the reference page can be used. Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfate, thiourea smerkabuto compounds, rhodania); reducing substances (e.g., stannous salts, amines); , hydrazine crocodile conductor,
Reduction sensitization method using formamidine sulfinic acid, silane compound] Rich noble metal compounds (for example, total complex salts, p
t. Noble metal sensitization methods using complex salts of metals of group (I) of the periodic table such as Ir and Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri, during production, storage, or line photographic processing of light-sensitive materials, or for stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted compounds); heterocyclic mercapto compounds such as mercaptothiazoles, mercapto Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (% l-phenyl-!-mercaptotetrazole), mercadetopyrimidine 7; Terocyclic mercapto compounds; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (particularly Hiro-hydro cI+?cy substituted (/, J, ja, 7)
tetraazaindenes); benzenethiosulfonic acids;
A number of compounds known as anti-capri agents or stabilizers can be added, such as benzenesulfinic acid enrichers and the like. The anti-capri agent or stabilizer is usually added after chemical sensitization, but preferably during chemical ripening or before the start of chemical ripening. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time,
Preferably from the beginning! within the time period up to O whisper, more preferably within the time period up to co O-]. Specific examples include k-do-aq-cyazaindene compounds, benzotriazole compounds, and heterocyclic compounds substituted with at least one mercapto group and having at least one aza nitrogen atom in the molecule. Examples of antifoggants or stabilizers used in the present invention will be listed below, but the invention is not limited thereto. [-/ Reference-hydroxy-4-methyl-7,3゜3a
, 7-tetraazaindene ■-J 4A-human aq C/ , j, J a,
7-tetraazaindene ■-31-hydroxy-4-methyl-! ,Ko. Ja, 7-tet2azaindene ■-da --hydroxy-4-phenyl/, J. Ja, 7-tetraazaindene 1-z-methyl-1-hydroxy-/, J. Ja, 7-tetraazaindene II-j, J, 4-dimethyl-derhydroxy-7゜J
, Ja, 7-tetraazaindene 1-7 San-hydradPcy! -ethyl-4-methyl-/, J, Jm, 7-tetraazaindene 11-r, t-dimethyl-hydroxy-! −
Echirou/, J, Jm,? -tetraazainden...-ta benzotriazole 1-107-methyl-benzotriazole 1-tit-
Nitro-4-chlorobenzotriazole 1-/j ...-77 H 1-/1 1-/f The silver halide photographic emulsion of the present invention contains color couplers such as cyan coupler, magenta coupler, and yellow coupler.
It can include a coupler and a compound that disperses the coupler. A specific example is Research Disclosure (RD) 4
774$3. ■-c-GK is described in the patent. As yellow couplers, for example, U.S. Patent No. J,
PI3.10/No. DA, No. 622,420, No. 1 of the same
．． JJt, oco vol., same issue, vol. 0/. No. 7J2, Percentage No. 777-10739, British Patent No. 1
, 4A2j, No. 020, No. 1,174.740, etc. are preferred. As the magenta kabutsu, compounds of I-virazone type and pyrazoloazole type are preferable, and US Pat.
o, tip issue, same issue -, JJt. No. 197, European Patent No. 71,414, US Patent No. J,
at/, Da JJ No. J, 721. at No. 7, Research Disclosure JEJ $ J JO (/ril
31112 No. 10-31, Research Disclosure A-4! Ko30 (January 2013),
JP-A-40-4434$2, U.S. Patent No. 100,
Particularly preferred are those described in No. 410, No. 1, No. I, No. Tza, etc. Cyan couplers include phenolic and hinaphthol couplers, which are covered by the first US patent. No. 012.271, No. 012.271, /$4. JP Bue Dou No. 3,
JJr, JJJ issue, same No.-9Jri 4. -1oO No. J
, JjP, PJP No. 2, 10/. No. 171, No. 2,771,741, No. 1°fF7
．． rJJ No. 1,772,002, No. 3, 7!
T, No. 301, No. 301, ! ! -1O/7, No. 1, J
J7,777, West German Patent Publication No. J, J Kota, No. 7, European Patent No. 1 J/. J41A, U.S. Patent No. J, $41. Buichi No. 2, Same No.-
, JJ! , Tuck No. ≠, 41/, jIf No. 9 J7.7J7, European Patent No. #/, jJt Person No., etc. are preferred. Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure A/74 Reference J.
- Section G, U.S. Patent No. 1/41°470,! f#kai No. 77-19111J, USA 41! = ○a, oOa, ri JP No. 44. /11.2jtr, British Patent No. 1
．． No. 444,141 is preferred. Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 744. Co J7, British Patent No. 1. /Ko!
,! No. 70, European Patent No. 4. ! No. 70 and West German Patent No. 3,2 JIA, No. 111 are preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 1, Ax, Sty, Jr., British Patent No. 2,10, No. 773, etc. Couplers releasing photographically useful residues may also be used during coupling. DIR couplers releasing development inhibitors are described in RD/741J1■-F and are disclosed in the companion patents, JP-A Showa 17-/! ldeaX No. 77-/J
4A Ko3da, same t. Those described in U.S. Patent No. 41 are preferred. Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. JJt, No. 111, Tokukai Sho! Tar/1741
No. 1 and those described in IP-1701440 are preferred. In addition, examples of couplers that can be used in the photographic material using the halogen chain photographic emulsion of the present invention include the competitive couplers described in U.S. Pat. 4A7j No. 44.JJt, 3
P3, same No. 44. Examples thereof include multi-equivalent couplers described in Jlo, No. 411, etc., and couplers that release a dye that recovers color after separation as described in European Patent No. 1'13,302A. The couplers used in the silver halide photographic emulsion of the present invention are:
It can be introduced into the photosensitive 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. The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in US Pat. No. 4',/P. No. 313, West German Patent Application (OL8) No. 2. Art/. It is described in Core≠No. Appropriate special holidays that can be used in the silver halide photographic emulsion of the present invention are, for example, RD, A/ 74 μ3 on page, and 4/r7/4 on page 4 $7 from the right column to the left column on tar page. Are listed. The silver halide emulsion used in the present invention may contain other additives in moderation. That is, surfactants, hardeners, thickeners, dyes, ultraviolet absorbers, antistatic agents, brighteners, desensitizers, developers, antifading agents, mordants, and the like can be used. These additives are described in Research Disclosure Magazine (R, E8ERCHDI8CLO8URE. RD-/74443), vol./74.9age.
Coco~J/ (December, /ri71), “The
Theory of the Photographic Process 1st Edition J (THE)i) iEORY OF THEP
HOTOGRAPHIC PROCESS, 4cth
Ed,) Tee Age Aim y, (T, HoJ
ames) (/P77s Macmillan Publishing Co.
, Inc.). The binder used in the silver halide emulsion to which the present invention is applied is preferably gelatin (lime-treated gelatin, acid-treated gelatin, etc.), but in addition to gelatin, derivative gelatin such as phthalated gelatin, aldimine, agar, gum arabic, Cellulose derivatives, polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc. are used. Examples of halogen silver photographic materials that can be used in the present invention include color positive film, color beno film, color negative film, and color reversal film (if it contains a coupler). Photographic light-sensitive materials for plate making, light-sensitive materials for cathode ray tube displays (e.g. emulsion X-ray recording materials, materials for direct and indirect photography using screens)
, silver salt diffusion transfer process x (8i1ver 5altd
lffusion transfer 9roce
ss), MA optical materials for color diffusion transfer processes, photosensitive materials for heat development, etc. Color photographs using the silver halide photographic emulsion of the present invention It can be developed by a conventional method. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline water bath solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phinidine diamine compounds are preferably used, and a representative example thereof is 3-methyl-thin-amino-N,N-diethylaniline. , J-methyl-thin-amino-N-ethyl-N
-β-Human acetylaniline 3-methyl-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of the compounds of Kohori et al. can be used in combination depending on the purpose. The color developing solution contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It is common to include development inhibitors or anticapri agents such as benzothiazoles, benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfone R, tl ethylene cyanine (/, diazabicyclo [co. 2.2] octane), organic preservatives such as ethylene glycol, diethylene glycol, IJ, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, sodium Examples include fogging agents such as boron hydride, auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarmenic acid, aminopolyphosphonic acid, aluminum phosphonic acid, and phosphonocarboxylic acids. various chelating agents,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclodiaminetetraacetic acid, hydroxyethyliminodiacetic acid L/-hydroxyethylidene-/, l-diphosphonic acid, nitric a-N,
N,N-)rimethylenephosphonic acid, ethylenediamine-
Representative examples include N,N,N,/N/-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof. When implementing the magnification reversal theory, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroquine benzenes such as Hyde C1, l-phenyl-3-
Known black and white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The pH of these color developing solutions and black and white developing solutions is generally 2 to 12. The amount of replenishment of these developers depends on the color photographic material to be processed, but in general,
a 31 or less per 7 square meters of original material 69, by reducing the bromide ion concentration in the replenisher! 0
It can also be set to 0- or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and to use means to suppress the accumulation of bromide ions in the secondary developer. It is also possible to reduce the amount of replenishment. The photographic emulsion layer after θ development is usually bleached. The bleaching process may be carried out simultaneously with the fixing process, and Cf1
(I white fixing process) may be performed separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, further processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. Bleaching treatment after treatment can also be optionally carried out depending on the purpose. As a bleaching agent, for example, iron (II), copal)
Compounds of polyvalent metals such as (III), chromium (■), and steel (U), peracids, neutral compounds, nitro compounds, and the like are used. Typical bleaching agents include ferricyanide; ferric acid I
xB Organic complex salts of iron (m) or cobalt (1), such as aminopolymers such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, fluorohexanediaminetetraacetic acid, methyliminodiacetic acid, l,3-cyainodecpanetetraacetic acid, glycol ether diaminetetraacetic acid, etc. Carboxylic acids or complex salts such as citric acid, tartaric acid, and sulfuric acid; rich persulfates; AX salts; permanganate salts; nitrobenzenes, and the like can be used. Among these, aminopolycarboxylic acid iron(m) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(1) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron aminopolycarboxylate (m
) Complex salts are particularly useful in both bleach and bleach-fix solutions. The pH of the bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron (Ml) complex salts is normal! ,! ~r, but it is also possible to process at an even lower pH for speeding up the process. Bleach accelerators may be used in the bleach solution, bleach-fix solution, and their prebaths if necessary. Specific examples of useful bleach accelerators are described in the following specification: US Bone Rod No. 3,111. tjt, West German patent No. 1
．． Kota 0,1/Ko issue, Tokukai Shoj! -2! , tJO issue, Research Disc a-Jar A/7. /JP issue (/f7
Compounds containing a mercapto group and a disulfide bond, such as those described in JP-A-Sho! TO-/440. /2
Thiazolidine derivatives described in No. 3; United States Patent No. J,
Thiourea derivatives described in No. 704, No. 111; JP-A-Sho!
r-/l, iodide salts described in Ko Jj; diethylene compounds in polio described in West German Patent No. 27141.4AJO; polyamine compounds described in Japanese Patent Publication No. 4AI-1134; bromide ions, etc. can be used. . Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat.
No. t, West Patent No. 1. Jto, via issue, JP-A-13-4
! , No. 430 are preferred. Additionally, U.S. Pat. ! ! Compounds described in Ko, No. 1344 are also preferred. These bleaching accelerators may be added to the photosensitive material, and these bleaching accelerators H
% is valid. Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred. 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. It can be set over a wide range, but the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is Jo
urnal of the 5ociety
of MotionPicture and T
e1evision Engineers Volume 1,
P, 2441-2! It can be obtained using the method described in J (/P!! Year J 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; however, due to the increase in the residence time of water in the tank, bacteria breed, and - the generated suspended matter adheres to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 3 is used very effectively. be able to. Tokukai Akira! t7-1.
Intiazolone compounds and cyabendazole compounds listed in JDA No. 2, chlorine-based disinfectants such as chlorinated sodium incyanurate, and other benzotriazole, etc., "Chemistry of repellents" by Hiroshi Horiguchi, edited by Sanitation Technology Society, " Sterilization, sterilization, and anti-mold technology of microorganisms”, “Encyclopedia of anti-bacterial and anti-mold agents” edited by the Japan Society of Antibacterial and Antifungal Agents
It is also possible to use the fungicides described in . The pH of the washing water in the processing of the photosensitive material of the present invention is ≠-
2, preferably 1-1. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the lIA source material, the application, etc., but in general 11CFi, /! -17@C for J7 seconds -1o minutes,
Preferably J! A range of 30 seconds to 1 minutes is selected for -30 sec. , Tokukai Sho! 7-r, !J issue,
! r-7th issue, 11th issue, Pu0-Jko0. J-san! All known methods described in this issue can be used. Further, following the water washing process, a further stabilization process may be performed, for example, color exposure for photography. Mention may be made of stabilizing baths containing formalin and surfactants, which are used as the final bath of the material. Various chelating agents and antifungal agents can also be added to the stabilizing bath for keratin. The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the iron removal process. 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. J, JIA Co., J.
Indoaniline compound described in No. 7, No. s, sex
, Zuri No. 2, Research Disclosure-114, 1
No. 10 and the same/! ,/! Ship base type compounds described in US Pat. No. 3,77P, metal salt complexes described in US Pat.
J-/J! , ≦1r can be mentioned. The silver halide color light-sensitive material of the present invention may contain various types of 7-phenyl-J, if necessary, for the purpose of promoting color development.
- Typical compound F that may contain pyrazolidones
I wait for Kaiaki! ≦-1μ, JJ issue, same! 7-/Gei, $74
C7 and the same zt-//! , Reference Jr., etc. are listed. The various processing solutions used in the present invention are typically kept at a temperature of 331CNJt"C, which is used in io'C-to'C. It is possible to achieve improved image quality and stability of the processing solution at lower temperatures.In order to save silver on photosensitive materials, West German Patent No. 14.770 or U.S. Patent No. 3. 71.4CP No. 5 Conort intensification or hydrogen peroxide intensification may be used. (Example) Examples are described below, but the invention is limited to these examples. Example 1 Emulsion layer (comparative example) Inert gelatin powder Of1 potassium bromide/7 in reaction vessel
t1 Potassium iodide/At%NH3 (27%) lOyxl
Dissolve in distilled water/if and stir the precipitated solution at 5011C. Silver nitrate here! An aqueous solution of Of and 200 td of an aqueous solution of potassium bromide/Jf were added at the same time for 2 minutes, ripened for JO minutes*m, and then acetic acid (
100w%) was added to 4AOd, and then silver nitrate was added to 100%
ft - Dissolve and precipitate solution t. Ogo and potassium bromide 7! An aqueous solution of t. With Otd? :9Br2. /l-Mamoru Nakara, 405HI
The mixture was added until the silver nitrate aqueous solution was used up. Thereafter, the emulsion was cooled to Jj'C, washed with water by a conventional quenching method, and then washed at 0'C at 984 J. After adjusting the pAg to 2.0, it was stored in a cool and dark place. The size of this particle is the circle equivalent diameter of the projected area, o, 7! μm
Met. Emulsion B (Invention) After adding acetic acid to the emulsion layer, it was prepared according to the following procedure. Sodium chloride! , -ft-added silver nitrate 10att-dissolved and precipitated solution AOOyd and added 1JOyd in /J minutes.Next, silver nitrate aqueous solution and potassium bromide 71ft-dissolved aqueous solution bu00ae and ykgBrs, rYt was maintained while silver nitrate aqueous solution was added in J7 minutes. The remaining silver nitrate aqueous solution was added for t-20 minutes while changing to pBrJ and maintaining this value. The following steps are the same as those for emulsion A. Emulsion C (present invention) When grains were grown in emulsion nlc while maintaining pBri, t, they were grown at t-9BrJ,/. Emulsion D (In the emulsion layer of the present invention, after adding acetic acid, aS, sodium chloride, and Jft were added according to the following procedure, and an aqueous solution containing 10t of silver nitrate was added at a rate of 400 d1!tlJ/Jayst for 73 min.). Aqueous solution of ?4
00d was added in 1 minute, the hole diameter was increased, and the aqueous solution was aged for 71 minutes. Then, while maintaining the silver nitrate aqueous solution and the potassium bromide aqueous solution t-pBrJ, /, the silver nitrate aqueous solution was added for 47 minutes (until it became narrow). The following is the same as the emulsion layer. After adding J, jxlo-'mol to EmAND for color XI-//l-silver/mol, sodium thiosulfate and chloroauric acid were added to @c. Optimal chemical sensitization was carried out using potassium and potassium thiophanate. In B m B - D, the emulsions were sampled at the point where the amount of added silver nitrate was 7 tons, and after centrifugation to remove gelatin, they were sampled with soO"c. When this sample was analyzed with E8CA, almost all of the added sodium chloride was present in all samples (2 of the added amount).
! ≦ or more) were deposited as silver salts. In addition, the final particles were similarly analyzed to calculate the chloride content and halogen conversion rate. The chemically sensitized emulsion was coated on a triacetylcellulose support according to the recipe shown below. (1) Emulsion layer O emulsion-Em-A#D (Silver, /X10-"% to 7m2) O coupler (/, jXlo-"Mo to 7m") o Tricresyl phosphate (/, /Of/ m”) O gelatin (J, 3017m) (2)
Protective layer Oko, 4! -Dichlorotriazine-bu-Hydro Nakashi 3
- Triazine sodium salt (o, otf/m") 0 gelatin (/, It) 17m) Coated samples were prepared under conditions of 70% relative humidity in C2.
Leave it for an hour.9. The pressure characteristics were evaluated as follows. Under humidity control conditions of 80% relative humidity, the coated sample was fixed at one end with the emulsion side facing inside, and bent along a stainless steel pipe with a diameter of tammm at a bending speed of 340"/10@ rotation at a bending speed of 340" for 7 seconds. -Bending is exposed10
This was carried out 10 seconds after exposure. Exposure was carried out through a continuous wedge for 17 ioo seconds, and the next color development section 11t was carried out. Measure the concentration of the treated sample using a green filter.9. Therefore, the image processing for the second son should be done with Jr"C under the following conditions. 1 Color development......2 Dansin! seconds 2
1! White・・・・・・・・・4 minutes 30 seconds 3 Washing・・・・・・・・・3 minutes 71 seconds 4 constant
Wear......... for minutes 30 seconds Wash with water......3 minutes! Second 6 Stable
・・・・・・・・・・・・3 minutes! The composition of the treatment liquid used in each step is as follows. Color current liquid sodium nitrilotriacetate /, Of sodium sulfite ≠, Of sodium carbonate JO0Of potassium bromide
t,athydrosilane sulfate
Ko, the person in charge? Hiro-(N-ethyl-N-β-hydroxyethylamino)-4-methyl-aniline sulfuric acid @##1 Add water /1 Bleach solution Ammonium tto,ot Aqueous ammonia (corr whisper) 2! , Od ethylenediamine-tetraacetic acid sodium iron salt iso in glacial acetic acid
add l-d water
/1 Fixer Sodium Tetrapolyphosphate a, OtSodium Sulfite -, of,, Thiosulfate 7
Nmo = Tsu A (70%) /7! , Otd sodium bisulfite ginseng, add 6f water
/J stabilizer formalin! Add r, Od water and evaluate the sensitivity and fog in the 9 parts where /A' bends in the t row and the parts where the t row is not done.9. The relative value of the reciprocal of the amount of 11 elements required for the optical density to reach the fog plus O0l is shown as the sensitivity. The results thus obtained are shown in Table 7. As can be seen from these results, the pressure fog can be improved by depositing Aga inside the particles and then performing conversion. The halogen conversion rate of the cargo is 40%.
It can be seen that fog caused by additional pressure is improved. Example 2 Emulsion E (Comparative Example) Inert gelatin of, potassium bromide/7 in reaction vessel
f1 potassium iodide fym/if%NH3 (Jj rumor)≠0xl
9 bottles of solution t-t dissolved in t-distilled water/l. Stir with @C. Dissolve silver nitrate toy here - 9 bottles solution - 200yptl
and potassium bromide/Jft-dissolved in water were added simultaneously over 2 minutes, physical ripening was performed for 20 minutes, then vinegar rR (100"N%) t-44OMl was added, and then silver nitrate 100ft- Dissolved aqueous solution t. and potassium bromide coat at and potassium iodide 1ft-dissolved nine bottles solution-〇〇yd in pBr
The silver nitrate aqueous solution was added while maintaining J and l until the silver nitrate aqueous solution disappeared. Thereafter, the emulsion was cooled to a temperature of 70°C, washed with water using a conventional 70% nitride method, and washed with water.
After conditioning, it was stored in a cool, dark place. Emulsion F (invention) Emulsion E was prepared by the following procedure after adding acetic acid. Sodium chloride! , 2ft-added, dissolved 1oat of silver nitrate and added 7JOtl of Niwaki solution in 73 minutes.
Next, the silver nitrate aqueous solution and potassium bromide zop@dissolved aqueous solution≠00- were added in 27 minutes while maintaining pBrJ, / until the silver nitrate aqueous solution f: 270d was consumed, and then the silver nitrate aqueous solution and bromide solution were added at the same pBr. potassium 2μ
? and potassium iodide/ff dissolved aqueous solution co00rd, p
The silver nitrate aqueous solution was added for 1°O minutes while maintaining BrJ, / until the silver nitrate aqueous solution was exhausted. Emulsion E%F was chemically and spectrally sensitized as in Example I. The sharpness was measured for the emulsion of Example 1 and the emulsion E%F of this example.
This was carried out by the method described in Applied Photographic Engineering, Vol. 4 (1)/-r (,/deto). However, only the current processing in this Example 1
It was done using the method. The MTF value was narrowed down to the emulsifier's value f100 and the relative value at 9 o'clock. Evaluation of pressure characteristics was carried out by the method of Example 19. Bilateral iodine was measured using B 8 CAt-. I will show these results to Ibarako. Comparing Em-A and Em-E, it can be seen that the sharpness improves as the surface becomes more iodine, and the pressure overlap becomes larger. By using the Comperjoy formulation in -Em-E, the sharpness was excellent and the pressure characteristics could be improved. Example 3 Emulsion G (Invention) The emulsion of Example 1 was prepared according to the following procedure after adding acetic acid, 4 ft of potassium thiocyanate was added, 1 oz of silver nitrate was dissolved, and 100 ml of the solution was heated to 130 ml in 13 minutes. Added. Next is the aforementioned salt! pBrJ
, silver nitrate aqueous solution t-270d in 17 minutes while maintaining t.
It was added until consumed, and then the remaining silver nitrate aqueous solution was added for 20 minutes while changing to p13r and l and keeping this constant. The following steps are the same as those for emulsifiers. As shown in Example 1, chemical sensitization and spectrally sensitization were performed using the specific gravity method, and 3]! Cloth friend. The pressure characteristics of this coated sample were evaluated by the method of Example 1. The results are shown in Table JK. It was found that pressure fog weathered even in emulsions in which halogen conversion was performed after thiocyanate was deposited inside the grains. Example 4 Sample No. 0/N107, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared on a base coated 9t-9 triacetic acid Celcouse film support. Em-A of and Em of Example
When applied to E and Em-Ft-7th layer (high sensitivity green-sensitive emulsion layer), the m-evil dye was changed to the dye shown below. (Composition of photosensitive layer) The coating amount was determined by silver halide and For colloidal silver, the amount is expressed in 97m" units of the bale, for Kab 2-1 additive and gelatin, the amount is expressed in 97m" units, and for sensitizing dyes, the amount is expressed in 97m" units of bale, and for sensitizing dyes, the amount is expressed in 97m" units of bale, and for sensitizing dyes, the amount is measured per mole of silver halide in the same layer. Indicated by the number of moles of intersection t. 7th layer (antihalation layer) Black colloidal silver...O0λ gelatin
・Skewer-/, JExM-9m--0
,0t UV-/...O,0SUV
-2...6. at UV-J @@fist 0.0bu8o
1v-/・-Φ0. /j8o1v
-ko ---0, /j8o1v-J
-*-0,0! 1st layer (middle layer) Gelatin.../, 0UV-/
・・・0.03ExC-Reference
...0.0 BxF-t
---o, you8o1v-/
@=0. /801v-J-
--0,/Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (A g I 8 mol-1 homogeneous g I type,
Equivalent sphere diameter 0.2μ, coefficient of variation of equivalent sphere diameter JO rumor, plate-like particles, diameter/thickness ratio 3. O] Coated silver amount ・・・・・・/, J Silver iodobromide emulsion (human gIj molar arc, uniform-AgI type, sphere equivalent @ 0.3 μ, coefficient of variation of sphere equivalent diameter l! rumor, spherical grains, Diameter/thickness ratio/, 0) Coated silver amount...0.4 Gelatin -...i,. Ex8-t---zxio-'Bx8
−J *= 1×10−”ExC-7
Fist・Fist 0.0I ExC-Co...0.20ExC
-J *...0.0JExC-p
---O, /JExC-1--
-0,0/ Third layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (11 molar mass, core-shell ratio l:l internal high-gI type, equivalent sphere diameter 0.7μ, equivalent sphere diameter Coefficient of variation/I%, plate-shaped particles, diameter/thickness ratio 1.0) Coated silver amount...0.7 Gelatin.../, 0BNB-/
---JXlo-'Exa-J
---J, JX/0-"BxC-a
---0,1/ExC-7--
-o, pz 1!5xc-a ---o
, oj8o1 Marl ・ ・−
0,0!8o1 Ma-J
Fist ・ ・ 0. OJhi 1st layer (middle layer) Gelatin...08ICpd-/
・@-0. /Solmar
...0. O! 1st layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI - molar ratio, = asinyl ratio /: 10
fi surface height AgIL spherical phase diameter 00Za, coefficient of variation of spherical equivalent diameter tZS, plate-like particle, diameter/thickness, 0) Coated silver amount......0. Jj Silver iodobromide emulsion (A g I J molar ratio, average human gIL sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter Jj ratio, spherical grains, diameter/thickness ratio 1.0) Coated silver amount... ... Ambiguous O, Ko O Gelatin Φ.../, 0Ex8-
J---zxio-'Ex8-s
---Jxto-'gx8-t
---/X10X10-4Ex
@Bruce・0. #ExM-2---0,07 ExM-10@*@0.0a2 BxY-// @@@0.018o
1 mar/ dispute...0. J8o1 Merzin...0. Oj 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Em-man, t of Example 1 or Example 10
Km-B or? ) Coated silver amount...0.1 Gelatin...0.2Ex8-J
---zxto-'Bx8-a
---5xio-'Ex8-t
---/X10"-'ExM-r
@war・0. JExM-ta...0
．． 0koExY-ti ---
o, osExC-co ---
0,0JEXM-/l --
-0,0/So l v-l
-Φ ・0.18o1v-44--*0.0/ rth layer (middle layer) Gelatin...08IC9d-
/ ...o, or8o1v-/
me-0,02 2nd layer (donor layer for multilayer effect on red-sensitive layer) Silver iodobromide emulsion (GI comol attack, internal high AgI type with core-shell ratio 2:l, equivalent sphere diameter /, 0 μ, equivalent sphere) Coefficient of variation in diameter 1j%, plate-like grains, diameter/thickness ratio 1.0) Coated silver amount...0.31 Silver iodobromide emulsion (AJiIJ molar arc, core shell ratio/:1
0 internal high AgI type, equivalent sphere diameter o, ats, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4.0) Coated silver amount... Tatami 0.20 Gelatin @ Temple O0! Ex8-J
・ ・ ・ rx/・0−'Ex
Y-/J ---0, //Ex
M-/J ・--0,03ExM
-ta @--o,/. 5olv-/am-0,-〇70th layer (yellow filter layer) Yellow colloidal silver...0.02 Gelatin...00ICpd-J
@-・0. /J8o1v-/
**・0. /JCod-/
...0.7O@// layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgIμ, J mole≦, uniform AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 7I% , plate-shaped particles, diameter/thickness ratio 7.0) - Coated silver amount ...0.
3 Silver iodobromide emulsion (A g I J mole ≦, homogeneous Ag I type,
Ball equivalent diameter 0.3μ, variation of ball equivalent diameter! ! Ko! -1 plate-like particles, diameter/thickness ratio 7.0) Coated silver amount ・Φ...0. /j Gelatin...1. BuEx8-4
・--koxio-'ExC-/bu
-@-0・0jExC-1---0,1
0 ExC-s ---o, oaBx
Y-/J m-@0.07BxY-/
z bone@@/, 08o1v-/
**-**J. First co-layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgIz0 mol-1 internal high AgI type, equivalent sphere diameter /, 0 μ, coefficient of variation of equivalent sphere diameter -! tower, multi-twinned plate-like grains , diameter/thickness ratio 2.0) Coated silver amount...O,j Gelatin ・No.・O6! Exa-
t---txto-'ExY-is
---o, a. ExY-7J meeting...0.018o1
v-/ @@@0.10 13th layer (
7th protective layer] Gelatin...00rUV-da...o, 1UV-z
...Q, /j8o1v-t
x-o, ot8o1v-2---0,01 1st layer

[First layer]

Microparticle bromide chain pores - (AgI comol ≦ - average - AgI type, equivalent sphere diameter 0.07 μ) ・ 10,! Gelatin..." 0, *Reference I polymethyl methacrylate particle diameter 1.jμ, · 0.2 fl-t-, 0, 4th section Cpd-z...0.jC9d-
j...0.1 In addition to the above components, each layer contains an emulsion stabilizer CGId-J (0,01-9
7m) Surfactant Cpd-4C (0.02f/m”
) is added as a coating aid. UV-t HOtBu UV-2 HO tBu tBu UV-Gas (x/ys7/J (weight ratio)) UV-r 8o1v-/ Tricresyl phosphate 8o1v- Diptyl cophthalate o1v-J 8o1v-Gas (SuC!! '1 t C0OHp
d-1 H pd-J H pd-41 C9d-1゛H)i pd-a xC-2 ExC-J 80H2C) 12Co2C) i3 ExC-藝NaO,8803Na xC-j ExC-4 ExC-7 xM-r α x j Q m=xJj ii1' x J , 1 mol, wt, about ay, oOa xM-2 α xM-10 ExY-// ExM-/2 ExY-/J EXM-/ HiroExY-/j 8CH, Cl-1, CO□CH3 Ex8-/ x8-J Ax8-J (C)i2)48u3Nu Exa-≠ Exa-1 Exa-Otsu (CH2) 4So3” (H2), $(J31Na
H-/CM, -CH-802-C)12-CONH-C)i. C)l=CH-190□-CH,-CONH-C)i
. PxF-/These samples 10/N103t-100 by white light
M8% Exposure for 17,100 seconds was applied, development was performed in the same manner as in Example 1 (however, the color development time was !'/j"), and when the magenta color density was measured, the exposure amount gave a fog of 10 and a J density. The sensitivity relationship was investigated and expressed as a relative value of sample 10/sensitivity FIL''Ii:100. The pressure characteristics were evaluated as follows. Under humidity control conditions of relative humidity reference OS, applying a load of a metal needle JIC20f with an emulsion surface of 1kO01mm, 10cII&/m
This process was performed before exposure. Furthermore, a test of bending along the stainless steel pipe shown in Example 9 was also conducted. At this time, changes in magenta density in the fogged area were measured using a microdensitometer. Evaluation of sharpness was carried out according to the method of Example 9. These results! - Shown in Table D. As is clear from the appearance, it was found that by using the emulsion according to the present invention, a sensitive material with high sharpness and excellent pressure resistance could be obtained. Example 5 Sample 0/20-2, which is a multilayer color photographic material consisting of each layer having the composition shown below on a subbed cellulose triacetate film support, was prepared. Here, BmA and grr knee D of Example 1 are
layer (first red-sensitive emulsion layer). At that time, the sensitizing dye is
The dye was changed to the one shown below. 7th layer; antihalation layer black colloidal silver ・・・・・・・・・・・・・・・・・・
... Silver 0. /r Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 00aO 2nd layer, middle class, J-T-KentadecylhydroΦnon ・・・・・・・・・・・・・・・...
・・−0, /rEx−/ −−−”=・−”−=”
−”・ 0.07EX-s ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ O,
0aU-/ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ a,orU-
1・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ o, orHB8-/
・・・・・・・・・・・・・・・・・・・・・・・・・・・
・0.10HB8-1・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ O0O cogelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ /, 3rd layer (7th layer) in 04
Red-sensitive emulsion layer] Silver iodobromide emulsion (Em-A or Km-D of Example 1) ・・・・・・・・・・・・ Silver O0! ! Sensitizing dye l ・・・・・・・・・・・・・・・
...Bu,riX/0-'sensitizing dye n ---
−−・・・・・・・・・・・・・・・・・・／、tXlo−
“Sensitizing dye■ ・・・・・・・・・・・・・・・・・・
・・・J, /X10 sensitizing dye■ ・・・・・・・・・・・・
......u, 0x10EX-2...
・・・・・・・・・・・・・・・・・・・・・・・・
...-o, sz. HB8-/ …・−・・−・…・Su・・・・−・
・・φ・・・-o, oozEX-ii ・------
…−−−−−−−−−−−−−−−−−−−o, o
or gelatin ・・・・・・・・・・・・・・・・・・
......... ) --------... Silver 1.
-〇Sensitizing dye I・・・・・・・・・・・・・・・・・・
...j, /'I:10-'sensitized color cumulative n -...
・・・・・・・・・・・・・・・-/, 4CX/) Sensitizing dye■ ・・・・・・・・・・・・・・・・・・-・JX10-' Increased color accumulation ■”・・・・・・・・・・・・−・
...J,OX/6-! IBX-J------
・・・・・・・・・・・・・・・・−・・・・・・・−
・o、5ayEX-s・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・-0
,010EX-10-・・・・・・・・・・・・・・・
・・・・・・・・・・・・-o, ooa)1B8-x
・・・・・・・・・・・・・・・・・・・・・・・・・・・
... o, oz. Gelatin ・・・・・・・・・・・・・・・・・・・・・
...
μ) −−−−−・・・・・・ Silver 1. BuO sensitizing dye■ ・・・・・・・・・・・・・・・・・・・・・! ,
-×10-" Sensitizing dye 1 [......
--"----t, a x t o -' sensitizing dye m
・・・・・・・・・・・・・・・・・・・・・J、＃
X10-'sensitizing dye■ ・・・・・・・・・・・・・・・
・・・・・・・・・1. /X10-"EX-z...
・・・・・・・・・・・・・・・・・・・・・・・・
... a,/! 0EX-J・・・・・・・・・・・・
・・・・・・・・・・・・－・・・・・・・・・・・・・・・ o
, artEX-3 ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ o, ot. EX-ti････････････････････････････････････････････････････
・・o、oarHB 8-i ・・・・・・・・・
・・・・・・・・・−・−・・・・・・・ o, 3 cogelatin ・・・・・・・・・・・・・・・・・・・・・
−・・・・・・・−／、! Jth layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・-/, O4 7th layer (first green-sensitive emulsion layer) Silver bromide emulsion (N silver tride ≦ so, average grain size o, tμfl@) ham ham se
e Silver σ, San〇 Sensitizing dye V...-"-----
−−−−−−−−−−s, z x to −' Sensitizing dye Vl ""..." r, o X
/ o -' Sensitizing dye■ ・・・・・・・・・・・・・
・・・・・・・・・J,0XiO-'EX-4・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・ O, Kobu0EX-t-・・・◆・・・・・・
・・・・・・・・・・・・・・・・・・ o, 02/EX-
7・・・・・・・・・・・・・・・－・・・・・・・Conflict・・・・
・・・-1... 0.01”0EX-r ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.02! HB8-/-・・・・・・・・・・・・
・・・・・・・・・・・・・・・ o, io. Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0.71 rth layer (second green-sensitive emulsion layer) 1 silver bromide emulsion (M silver fluoride, average grain size o, rzμ) -・・・・・・・ Silver o, t. Sensitizing dye V
---J, /X/0 sensitizing dye Vl''==
−7, ox i. Sensitizing dye■ ・・・・・・・・・・・・・・・・・・
・・tX10−'EX−4−・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ 0.
/jOE X −r −−−−−−−−−−−−−
−−−−−−−−−−−−−−−−−−o, o
t. E
−−−−−−−−−−−−−−−−o , o o
tEX-7・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0.0/2) iB 8
- / ・・・・・・・・・・・・・・・・・・
・・・・・・・・・−0,10 gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・／
, 10 second layer (third green-sensitive emulsion layer) Silver bromide emulsion (silver chloride 11 mol, average grain size /, Jμ) ... silver /, J sensitizing dye V ・・・・・・・・・・・・・・・・・・・-J,
! X10-”sensitizing dye■ ・・・・・・・・・・・・・
・・・・・・・・・1.0X10””sensitizing dye■ ・・・
・・・・・・・・・・・・・・・J, 0X10-
'EX-g ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0,041EX-t
・・・・・・・・・・・・・・・・・・・・・－・・
......-0,021HB8-ko ......
・・・・・・－・・・・・・・・・・・・・・・・・・ 0.
22 Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・－・・・・・・・ /, 7 da 1st O layer (yellow filter layer) Yellow colloidal silver ・・・・・・・・・−・*@11 +
a* oss silver 0.0! J, j-G t-pentadecylhide a middle non ・・・・・・・・・Fist・・・・・・
・・・-00aS gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ Oori I
1st/Layer (1st emulsion layer) Silver bromide emulsion (M silver fluoride r moles, average grain size 0.1μ) ・・・・・・・・・・・・ Silver O, Co Sensitizing dye■ ・・・・・・Old・・・Old...
・・0. jXlo-'EX-2・-・・e・・・・1
Old...
r・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・-0,12HB8-t ------
−−−−−−−−−−−−−−−−−−−−−−−−−
o, Jt gelatin ・・・・・・・・・・・・・・・・・・
・・・e@e・・・・・・ 1. 1st J layer (first back emulsion layer) Silver bromide emulsion (silver nitride 10 mol, average grain size 1.0μ) ・・・・・・ Silver O, Da J
Sensitizing dye■ ・・・・・・・・・・・・・・・・・・
...Ko, 1xio-'EX-2...
・・・・・・・・・・・・Old・・・・・・・・・ o, J. HB8-t ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0.0! Gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
... O1 藝 4 1st J layer (3rd sensitized emulsion layer - silver bromide emulsion ('M9 @i0 mole 1 average grain size /, Iμ) ... Silver 0.77 Sensitizing dye■ ・・・・・・・・・・・・・・・・・・・・・
Ko, 2X10'''EX-2......φ...
...@@1111@Rin... O, JOHB
8-t -,,------・・・・・・・・・・・・-
・・・・・・ 0.07 gelatin ・・・・・・・・・
…*ae oss trout・・・・−・…−0,≦7th layer (first protective layer) Silver bromide emulsion (silver bromide 1 mol, average grain size 0.07μ) − ---・・・・・・ Silver 00
IU-t −−−−−−−−−−−・−−−−−
−−−−−−−−−−−−−−−−−o, tiU−=
2・・・・・・・・・・・・・・・・・・・・・・・・Fist・・・・・・・−0, /7HB8−/ −・・・・・・・
・・・－・・・・・・・・・・・・・・・－－－－－－－0,
ri0 gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・-i, o. 17th layer (Jth protective layer) Polymethyl acrylate particles (1.!μm in diameter) - 0.2-
8-／ ・・・・・・・・・・・・・−・…………・Axis・
・・・ 0 @ 02S-1・・・・・・・・・・・・
・・・・・・・・・・・・・・・φ・・・・・・・・・-o
, J. Gelatin ・・・・・・・・・・・・・・・・・・・・・
.....-0.7J In addition to the above-mentioned components, a gelatin hardening agent H-/ and a surfactant were added to each layer. The chemical structural formulas or chemical names of the compounds used in the present invention are shown below. EX-t α EX-CoEX-5 803Na 8L) 3Na EX-Reference H υ8 to 17 (SUEX-7゜EX-// Drama === Drama HB3-/ Tricresyl Phosphate) 1B8-
2 Digtylphthalate sensitizing dye ■ 8-/8-1 C2) 1° (C) 12) 4803e (C) 12) These samples were added to 4S03 under conditions of ao”c and relative elasticity of 70%. After leaving it for a while, fix one end with the emulsion side inside, and fix the diameter t.
I bent it along the omm stainless steel pipe/10@ while rotating it. Thereafter, the same in-situ treatment as in Example 1 was carried out, and the change in fog density at the folded portion of the cyan image was measured. Table out the obtained results! Shown below. The emulsions of the present invention reduced the increase in pressure fog. Table-! Comparative Example 6 of Change in Fog Density at Bending Area Samples 30/J0, which are multilayer color photographic materials, were prepared on a cellulose triacetate film support coated with an undercoat and having the composition shown below. Examples/(Q E m -A and E m -
D @1st/layer (blue-sensitive emulsion layer) K was applied. At that time, the sensitizing dye was changed to the dye shown below. Composition of photosensitive layer> For silver halide and colloidal silver, the coating amount is the amount expressed in f/m2 of silver, nine couplers, additives,
and for gelatin, the amount expressed in t/m”,
For 9 sensitizing dyes, it is expressed as the number of moles of silver halide 7 moles 61 in the same layer. - 1st layer: antihalation layer black colloidal silver silver 0.37U-10,
027 U-Jo, ozz U-Jo, 04≠ HB8-j 06074 gelati y 2. r/1st layer: middle layer U-to, o core U-1 0.02 da U-jO
00&! HB8-J 00074 Gelatin 1. ! 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion Silver 00-3 Silver iodobromide emulsion Silver 0. //Silver iodobromide emulsion
Silver O0! ! Sensitized color line 1 a
, 7xto-3C-io, / C-20, / J C-Jo, or C-to, or HB8-/ 0.06HBS-
x o, 1sC-100, /4
4 Gelatin /, 44th layer:
First red-sensitive emulsion layer Silver iodobromide emulsion Silver 0.73 sensitizing dye I
a, oxto-3C-10,17 C-J O,
Ko rC-30,07 C-Hiroshi 00l
lHBS-/0.
/koHBS-1 0.
Koda C-10o, oot gelatin 2.34 in the jth layer:
Middle layer gelatin 0. Octopus Cpd-/
o,t. HB8-/0.01! Dye 1 0.071U-Reference
〇, 02JU-40,036 HB8-da 7.7×10-3 Layer: First green-sensitive emulsion layer Silver iodobromide emulsion Silver O0≠r sensitized color accumulation I
I s, txto-” sensitizing dye [1/
, ) × 10-” C-40, JJ C-70,077 HB8-10. Co? Gelatin /, /J No. 71: λth green-sensitive emulsion layer Silver iodobromide emulsion Silver o, xi Silver iodobromide emulsion Silver 0.0% silver iodobromide emulsion
Silver O0X sensitizing dye ■ Ko,
ko×10-3 sensitizing dye■ t, oxto
-”C-t O, Ko0C-
1f 0.
07IC-≠ 0.07riC-t o
, o3tHB8-/
0,/l gelatin 0.7
2nd layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion Silver O0 sensitized color layer ■
1,4X/(7-'sensitizing dye■
ko, /X10-' sensitizing dye V J, ≦
×to-”C-40,034 C-I O,0ko0HBS-
/ 0.032 gelatin
0.3 da 2nd layer: yellow filter layer yellow comid silver silver 0.3 da. //Cpd-/
0.2tHBS-
/ o, tz Gelatin /, /P 1st layer sensitizing dye-V t. yxto-3C-2
0.12C-//
0,10HBS-70,-1 gelatin 0. rj 11th layer: 1st green-sensitive emulsion silver iodobromide emulsion (sensitizing dye Vt silver 0./7J.0X
Silver iodochlorobromide emulsion Silver O0λl (Em-A
(Em-D) Sensitizing dye-■ Reference X/l)='c-r
o, Jr c-4A o, o
Hiroda) IB8-t o
, t. Gelatin 0.71 1st J layer:
First protective layer gelatin 0.10U-ref.
〇, 10U-to, tz HBS-san 〇, OJJ dye 1
0. /J" 1st J layer: 1st protection layer polymethyl methacrylate particles 0./4A diameter approx. 1
．． In addition to the above composition, a gelatin hardening agent H-7 and a surfactant were added to each layer of Jμm gelatin 0 and r7. The structural formula of the hazardous compound used is shown below. Sensitizing dye. -7 C,)l, (S. -J U-≠ u-1 Dye I 803 Na C-/ -J (gc, hll -J C-r C-ta' l-13 Cpd-/ CH,, C) l-80, -CI-12C (JNH-C)
i. C)i,=mC)1-802-CH2-CONH-C)
i. ) 1B8-/tricresyl phosphate) iB8-dioctyl phthalate HBS-J dibutyl phthalate) 1B8-Hiroshi his(1-ethylhexyl phthalate) After allowing it to stand for some time, the entire continuous wedge was exposed for 10 seconds and developed in the same way as in Example 3 to obtain characteristic curves for cyan, maze/yellow, and yellow a-colors.About the characteristic curve for yellow color images The fog density is 0./The reciprocal of the exposure amount that gives a high optical density is expressed as relative sensitivity.Evaluation of pressure characteristics is performed as follows9.Relative humidity 〇%
The coated sample was fixed under wet conditions with the emulsion side facing upward, and the emulsion surface was scratched with a metal needle having a diameter of 0.1 n@m. At this time, a load of 20 f was applied on the metal needle. Scratching with this metal needle was performed before development, and the change in yellow density in the scratched areas was measured using a microdensitometer and compared. The results obtained are shown in Table-1. Comparison of Pressure Characteristics and Sensitivity The emulsion of the present invention makes it possible to suppress the increase in capri due to scratching without reducing sensitivity. Example 7 Each of the compositions shown below was coated on a cellulose triacetate film support after being primed. - Sample 440/~4AOJt, which is a different multilayer photographic material, was prepared. Here, EmA of Example 1 and EmE, F of Example 20 were prepared.
t-Applicable to the 7th layer (high-sensitivity green-sensitive emulsion layer). that time,
The sensitizing dye was changed to the dye shown below. <Composition of photosensitive layer> The numbers corresponding to each component indicate the coating amount expressed in f/m'' units, and for silver halide, the coating amount is expressed in terms of silver.However, for sensitizing dyes, the same Coating amount is expressed in large mole units per mole of silver halide. 37 layers (antihalation layer) Black colloidal silver 0. Cogelatin Co, 6Cpd-s3
0. JSolv-Jj
σ, o-2 2nd layer (intermediate layer) Fine grain silver bromide (average particle size o, o 7μ) o, iz gelatin i,. 3rd layer (low-sensitivity red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide!, ! molar, average grain size 0)
．． 3μ, coefficient of variation related to particle size (hereinafter simply referred to as coefficient of variation) (%)! ,! gelatin
j, QEX8-3/2.0X
10-'Ex8-Jko /, 0x10
-4Ex8-33 0, JX/0
”'ExC-J/0.
7ExC-jko o, 1
ExC-340,0 Cpd-Jj 0.0
/8o1v-Jj 0.
18o1v-720,2 8o1v-J4CO, / Part III C high-sensitivity red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 3.1 mol%, average grain size 0
．． 7μ, coefficient of variation it%) /, J Gelatin 1. ! ExS-
J/5xto-'BX8-74
/,jxlo-'Bx8-JJ
O, LtX/ 0-'ExC-Jlfi
0.1! ExC-310,
0j ExC-3s o, asEx
C-360,0/8o1v-Jj 0.
0j8o1v-3-〇, J 1st layer (middle layer) Gelatin 01rC9d-
JJ O,0j8o1v-J
j O,0/th layer (low-sensitivity green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.3
μ, coefficient of variation ≦) O0 Hiroshige dispersed silver iodobromide emulsion (
Silver iodide 7 mol%, average grain size 0.2 μm)
o, 1 gelatin
J, 0Ex8-J4A/×10
-'Ex8-Jj 1x10-
'gx8-74 /x10''-'
ExM-Jta 0-koExM-3
70,44 ExM-000,/1 ExC-Jta 0.0j501v
-JJ/, J8o1v
-Jl-0,04t 8o1v-310,0/ 7th layer (highly sensitive green-sensitive emulsion layer) Polydisperse silver iodobromide emulsion (Em-A of Example 1 or Example 2
E m -E or F) 0. Tazerachi/
/・4Exa-34c
O, 7×10-'BXB-Jj 2.
rxlo-'Ex8-34 0.7x10
-'ExM-370,01 ExM-1fi0 0.04cEx
C-Jt o, oi8o1v-j
/ 0.0r8o1v-JJ
01S8o1v-j4c
O, 03rd layer (yellow filter layer) Yellow colloidal silver O, cogelatin
OoriCpd-JJ
0. Ko361v-Jko
0. /Second layer (low sensitivity blue-sensitive emulsion/I) Monodisperse silver iodobromide emulsion (silver iodide t molar ratio, average grain size 0.J
l, coefficient of variation JO Ha) O0 coefficient heavily dispersed silver iodobromide emulsion
Emulsion O, a described in Table r Gelatin 1. Ex8-77
/×10″′″4'EX8-3
1 /X10-'ExY-00
0,r BxY-thing/0. #ExC-
330,0! 8o1v-j 00U8o1v-
Su o, i io skin (high sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (Iodide molar concentration, average grain size 1.
! μ, coefficient of variation 111) 0. j gelatin
2. CoEx8-J7
z×io-'Ex8-11
1'110-5ExY-aOO,J ExY-藝10.2 ExC-JJ O,0
28o1v-JJ O
, /1st/layer (7th protective layer) Gelatin /, 0C9d-3
30, / C9d-J da 0.1cpa-J
t O, /Cpd-340, / 8o1v-Jl O, /8o1v
-1440, / First layer (first protective layer) Fine grain silver bromide emulsion O, Co! (Average particle size 0.07μ) Gelatin /, 0 Polymethyl methacrylate particles (diameter /, 1μ) O-1 Cpd-310,1 Additionally, surfactant Cpd-7 and hardening agent H-/ were added. Next. Ex8-j/ x8-JJ xa-JJ (C12)3803Na ExS-Jg (CH2)3Bo3- (Ck12)3803Na
X8-31 (C)12)4SO3Na x8-36 (CHt)s 5Os-(0M2)3808Nax8-
37 (C)12)3803- (CH2)380s Na
x8-31 ExC-34A (JC)i, CM, eONHcHzcH2 (JCOM3
xC-J7 ExC-J/ ExC-74 ExM-J7 ExM-san〇ExC-Jj ExY-san〇("1 ExC-3s (Exemplary compound person-7) H3 ExY-Sanno α ExC-jri (Exemplary compound A-10) f”N cpa-Jj H 9d-33 Cpd-J reference'C4) 1°Cpd-Jj C,H. Cpd-3A 8o1v-J/ 8o1v-j Ko8o1v-33 8o1v-jμ 8o1v-77 Cpd-77 Cpd-3r -t C)12=CH-80□-CM. C)12=CH-802-C)i. Using A light source for these samples, μ
After adjusting t00''KK and giving a maximum IOCM8 exposure source, the following color development process was performed to evaluate the photographic performance. These samples 〇IN≠03 were subjected to loCMS using white light.
% /// 00 second exposure was given and the same as in Example 1 (
However, the color development time is 3'l! “) development process,
When measuring the magenta color density, the fog is 10, and the sensitivity relationship is determined by the exposure amount that gives the J density. The sensitivity of sample 10/ is expressed as /DO and its relative value. The pressure characteristics were evaluated as follows. relative humidity a
O''S v!4 Under humid conditions, the emulsion surface was Q, a 111 mm metal needle was loaded with a coat and pulled at a speed of 037 min. This step was performed before exposure. Furthermore, a test was conducted in which the material was bent along the stainless steel sheet shown in Example 1.The change in magenta density at this time was measured using a microdensitometer.The sharpness was evaluated in Example 1. The results are shown in Table 7. It is clear that by using the emulsion of the present invention, a sensitive material with high sharpness and excellent pressure resistance can be obtained. Understood. Applicant for license: Fuji Photo Film Co., Ltd. Procedural Amendment 1, Indication of the case: 1985 Application for Expenses No. 2 tioat
No. 2, Name of the invention Silver halide photographic emulsion 3, Relationship with the person making the amendment Case Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact address 106 Minato-ku, Tokyo Nishiazabu 2
No. 26 Fuji Photo Film Co., Ltd. Tokyo Head Office Tel: (406) 2537 Table Target of amendment ``Detailed Description of the Invention'' section of the specification & Contents of amendment ``Detailed Description of the Invention'' section of the specification The description has been amended as follows. l) Correct "Scatter with high sensitivity" in line 13 of page 3 to "Capri with high sensitivity". 2) Correct the structural formula at the bottom of page 10 as follows. 3) No. J! Correct "Please make it so that it becomes 601s" on the page ≠ line to (make it so that it becomes -40%). 4) "Please make the following color development t-Jt-" on the 13th line from the bottom of the 14th co page. The color considerations are the same as in the examples. S) Insert the following after "Kotowa Gatsu 9." on the 3rd line of the 1st Hiro J page. "Example R The sample prepared in Example 3 was treated with toi-tosy IH white light to CMS, 1.90 seconds of light per ///oo seconds, and the same results as in Example Hiroshi were obtained. Table 1 Processing method step Processing time Processing temperature Color developing iron 3 minutes 73 seconds Jr0C Bleach 1 minute 0 seconds jr'c Bleach-fixing J minutes 1! seconds Jr'C Washing with water 11) 0 seconds Jj'C Washing with water (2
) 1 minute OO seconds JJ0C Stable 4co seconds JI 0C Dry 1 minute/j seconds 3100 Next, the composition of the treatment liquid is described. (Color developer solution) (Unit: t) Diethylenetriaminepentaacetic acid 1. . l-Hydroxyethylidene 3.0-/,/-
Sodium diphosphonate sulfite Hiroshi, 0 Potassium carbonate io,. Potassium bromide /, 4C potassium bromide /, j■Hydroxylamine sulfate 1. 4'-(N-ethyl-
N-(β-hydroxyethyl)aminoco-2-methylaniline sulfate! add water
/, OL, pH 10,0! (Bleach solution) (Unit f) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 1000 Ammonium bromide 100.0 Ammonium nitrate
10.0 Bleach accelerator o
, oat mol ammonia water (27%) tr
, add o water /, 0Lp
Hj, J (bleach-fix solution) (unit f) Ethylenediaminetetraacetic acid ferric ammonium dihydrate! 0.0 Ethylenediaminetetraacetic acid disodium salt 2.0 Sodium sulfite 1 O Ansonicum thiosulfate aqueous solution (70%) 0.0 ml Ammonia water (27%) Otsu, oy Add water
/ , 0L pH 7, J (Washing liquid) Tap water t-H type strong @ injection cation exchange resin (Amberley manufactured by Rohm and Haas) IR-/J17B) and OH
Type anion exchange resin (Amberly) IR-4c00
) Water was passed through a T-packed hotbed column to reduce the concentration of calcium and magnesium ions to 3/L or less, and then sodium incyanurate dichloride (0/L) and sodium sulfate were added to 1. jf/Lt-addition 90 The pH of this solution is in the range of t,j-7,1. (Stabilizing liquid) (Unit f) Formalin (37 sacs) 2.011Ll
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.02 Add water
/, 17L pH 7,0-1,0 Example 2 The next sample prepared according to Example 10/, 10Jf / with white light
After exposure for OCM8, / / / 00 seconds, the same results as in the example can be obtained by processing in the manner described below. Thorn - Processing method Step Processing time Processing temperature Color developing iron Comin 30 seconds 4co0c Bleach fixing J
minutes oo seconds san o 'c wash 111 J o
Seconds 3!0C water washing (2) 20 seconds Jj
'C stable 20 seconds Jj'C dry 6
10 seconds AJ-'C Next, the composition of the treatment liquid will be described. (Color developing solution) (Unit f) Diethylenetriaminepentaacetic acid, O7-hydroxyethylidene- /, /-diphosphonic acid 3.0 Sodium sulfite, O Potassium carbonate
30.0 Potassium Bromide
1. φ Potassium iodide /
, J-η Hydroxylamine sulfate λ, Reference-[N-ethyl-N-(β-hydroxyethyl)amino]-comethylaniline sulfate Da, j Add water
/,0LpH10,OJ (bleach-fix solution) (unit: t) Ethylenediaminetetraacetic acid ferric ammonium dihydrate! 0.0 ethylenethia di-sodium tetraacetate! , 0 Sodium sulfite 1, O Ammonium thiosulfate aqueous solution (717%) , Am Acetic acid (
ritgI)! , Oxl bleach accelerator with 0.01 mol water added
/, 0L pH 4.0 (Washing liquid) Tap water 'KH type strong acidic cation exchange resin - Amberlite IR-/CoOB manufactured by M&Haas Co., Ltd.) and OH type anion exchange resin (Amberlite IR-4400 manufactured by M&Haas)
was charged and water was passed through a mixed-bed system to reduce the concentration of calcium and magnesium ions to below t-3 da/L, followed by sodium incyanurate dichloride 2019/L and sodium sulfate/, jf/L' 90 pH of this solution by adding fl
is in the range of A, j-7,7. (Stabilizing liquid) (Unit f) Formalin (37Ls) λ, Om Polyoxyethylene-p-monononylphenyl nityl (average degree of polymerization 10) 0# Ethylenediaminetetraacetic acid disodium salt 0.0j Add water
/,0LpHz,or,.

Claims (1)

[Scope of Claims] 1) In a silver halide photographic emulsion comprising silver halide grains having a core/shell type structure, the core portion of the silver halide grains is a halide containing 10 to 45 mol% of silver iodide. A silver halide photographic emulsion comprising silver and having a silver halochloride layer, a silver thiocyanate layer, or a silver citrate layer partially converted to halogen inside the grains. 2) Silver iodide content on the surface of silver halide grains is 3 mol
% or more, the silver halide photographic emulsion according to claim 1.