JPS6326651A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to reduce heat fog by incorporating silver halide grains each having a specified crystal face on its surface and high silver iodide in the inside and one emulsion layer hardened by an organic hardener capable of reacting gelatin and releasing an acid. CONSTITUTION:Each of the silver halide grains has the crystal face defined by the Miller indices 331 on its outside surface, and it has a core/shell type structure composed of the surface made substantially of silver bromide or iodide, and the inside of the surface made of silver halide higher in the silver iodobromide content, and at least one of the emulsion layer contains said grains and hardened by the organic hardener capable of reacting with gelatin and releasing an organic or inorganic acid, thus permitting heat fog and desensitization due to the interimage effect to be reduced.

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver iodobromide photographic material with high sensitivity and low fog.

[Background of prior art and invention]

In recent years, demands on silver halide emulsions for photography have become increasingly strict, with increasingly high standards required for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and sufficiently high optical density. being done. In order to meet these demands, silver iodobromide emulsions containing 0 to 10 mol % of iodine are well known as high-sensitivity emulsions. Methods for preparing these emulsions include conventional methods such as ammonia method, neutral method, acidic method, etc. under pH conditions, p.
Methods for controlling Ag conditions and mixing methods include the single-noe method and the double-jet method. Conventionally, silver halide emulsions used in high-speed photographic films consist of polydisperse twin crystal grains. Silver iodobromide emulsions are known. Based on these known technologies, technological means up to the N level have been studied for the purpose of achieving further high sensitivity, improved graininess, high sharpness, and low sharpness (J, -'), and have been put into practical use. In the silver iodobromide emulsions targeted by the present invention, research has been conducted on emulsions in which not only the crystal habit and grain size distribution but also the iodine concentration distribution within individual silver halide grains are controlled. Sata. In order to achieve the above-mentioned photographic performance such as high sensitivity, excellent graininess, high sharpness, low density and sufficiently high covering power, the quantum efficiency of silver halide has been improved and Monodisperse emulsions are known that are aimed at efficiently achieving high sensitivity while maintaining low ζ in chemical ripening.
No. 58-126526, No. 59-29243,
According to No. 59-180536, No. 59-181:137, etc., the outer surface of the particle is a (100) crystal plane.
111) It is known that high sensitivity can be achieved by using a monodisperse emulsion consisting of cubic, octahedral or tetradecahedral silver iodobromide grains having crystal planes. Furthermore, JP-A No. 60-222842 discloses that silver iodobromide having a (110) crystal face can achieve a lower aging resistance. Recently, such conventionally known (100), (11
1) Silver bromide and silver iodide grains having crystal planes other than the (110) plane are disclosed in VF JP-A-61-83531. Regarding this new crystal plane, recent research has shown that (
331) was reported in the 1986 annual conference of Nippon Photo T, Research Presentation Abstracts, p. 79. In the process of researching silver iodobromide emulsions with (331) crystal planes as a means of high sensitivity, we discovered that the emulsions exhibit heat resistance (increasing of γ when photosensitive materials are stored at high temperatures). It was discovered that there was a problem with VF properties, and furthermore, using an organic hardener that reacts with gelatin to release organic or inorganic acids as a hardener for the gelatin used in the pineapple of the emulsion reduces heat fog, but the heat fog can be reduced. , multilayer structure (meaning that there are two or more coated layers with gelatin as the binder,
A commonly used silver halide photographic light-sensitive material has a multilayer structure including at least one gelatin-silver halide emulsion layer and a gelatin protective layer. ), the desensitization (
It was discovered that there is a lack of 5α with large layer desensitization).

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material having high sensitivity and low thermal burnout.Another object of the present invention is to provide a silver iodobromide emulsion layer having a (331) crystal plane. It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a high sensitivity and exhibits less thermal x-ray and double layer desensitization.

[Structure of the invention]

The object of the present invention is to have a core/shell structure in which at least the grain surface is substantially made of silver iodobromide, has a (331) crystal face on the outer surface, and has a higher silver iodobromide content inside than the grain surface. and at least one silver halide emulsion layer containing gelatin as a binder and hardened with an organic hardener that reacts with the gelatin to release an organic or inorganic acid. This can be achieved using a silver halide photographic material. The present invention will be explained in detail below. The halogenated particles related to the present invention have a Miller index (331
) on the outer surface, and at least the surface of the grain consists essentially of silver bromide or silver iodobromide. In addition to the (331) surface, the particle has a (100) surface.
It is acceptable for planes, (lit) planes, (110) planes, etc. to exist, but it is preferable that the ratio of (331) i7i'i to the total surface area is 20% or more, particularly 80% or more. preferable. Furthermore, the presence of (331) planes and their proportion can be determined by a method using an electron microscope, an x#a diffraction method, or a dye adsorption method. The silver halide emulsion layer of the present invention preferably contains silver halide grains having (331) planes in an amount of 30% by weight or more, more preferably 50% by weight or more. In the composition of the halogenated grains according to the present invention, "consisting essentially of silver bromide or silver iodobromide" means silver halides other than silver bromide and silver iodobromide, as long as the effects of the present invention are not impaired. , meaning that it may contain, for example, silver chloride. Specifically, in the case of silver chloride, the ratio is preferably 5 mol% or less, more preferably 1 mol% or less -1. The proportion of silver iodide in the subhalogenated grains according to the present invention is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 to 15 mol%. Even if the silver halide grains according to the present invention are silver halide grains of a single IF structure, they may be silver halide grains composed of a plurality of phases (for example, layers) having different halogen compositions (for example, core/
shell-type particles). When silver halide grains do not have a single silver halide composition, halogen inside the grain, llr& is silver chloride,
Silver chlorobromide or the like may also be used. Furthermore, the halogen composition within each phase may be uniform or may vary continuously. One of the most preferred forms is one with high iodine content inside the grains. That is, it is a silver halide grain having within the grain a phase (or phases) having a higher iodine content than the iodine content on the grain surface. Details of such a core/shell emulsion of the grain internal high silver iodide type having the (331) plane according to the present invention are described in JP-A-61-88235. In the case of such a core/el emulsion, the silver halide mra of the shell 7 preferably contains 3 to 40 mol % of silver iodide, and the silver halide mra of the shell 1 contains 0 to 10 mol % of silver iodide. The difference in silver iodide content between the shell and core is preferably 2 to 30 mol%.The change in silver iodide content at the core/shell boundary is as follows: It can be continuous, stepwise, etc. There are no particular restrictions on the grain size of the silver halide grains according to the present invention (preferably 0.1-3.
The present invention is at least effective within the range of 0μ countries. In addition,
In this specification, the grain size of silver halide refers to the length of one side of a parallelepiped that is equal to its volume. The silver halide grains according to the present invention are usually produced and used in a form dispersed in a dispersion medium such as gelatin, that is, in a form called an emulsion. The particle size distribution of the group of particles at this time may be monodisperse, polydisperse, or a mixture of these, and can be appropriately selected depending on the application. In order to produce silver halide grains having (331) planes according to the present invention, the method disclosed in JP-A-61-83531 can be used. That is, as a method for producing bromide grains or silver iodobromide grains having (331) planes, silver halide grains are produced by mixing a water-soluble salt solution and a water-soluble halide solution in the presence of a protective colloid. In the forming step, the 9AIF of the emulsion is controlled within the range of 8.0 to 9.5 during a period in which at least 30 mol% of the total silver halide is formed, and during this period, the following general formula ([ ), (■)
, (III) or (■) and a compound having a repeating unit represented by the following general formula (V). has been done. General formula (1) General formula (fl) General formula (ill) General formula (IV) General formula (
V) I5 -(-CI+, -C+- ■ In the formula, R11, R12 and I'l) may be the same or different, and each represents a hydrogen atom, a halogen atom, an ami7 group, a derivative of an ami7 group, a furkyl group, alkyl group derivative, aryl group, aryl group derivative, cycloalkyl group, cycloalkyl group derivative, mercapto group, mercapto group derivative or -CONII-R,, (R, is a hydrogen atom, Alkyl group, amide 7 group, alkyl group derivative,
Ami7 derivative, halogen atom, cycloalkyl group,
It represents a derivative of a cycloalkyl group, an aryl group, or an aryl group. ), RtS represents a hydrogen atom or an alkyl group; Formula (1), (II), (1) or (
1 obtained by removing one hydrogen atom from the compound represented by IV)
It represents a valent group (for example, one hydrogen atom removed from the R1-R13 or 011 moiety in the above general formulas (1) to (IV)), and J represents a divalent linking group. The amount of the crystal control compounds (1) to (V) to be added varies depending on the production conditions such as the desired silver halide grain size, emulsion temperature, pH, pAg, and silver iodide content. A range of 1 to 2 x 10"" moles of lO per mole is preferred. It should be noted that the tetrazaindene compound has the general formula (V
), the amount to be added is determined by the molar loss of the tetrazaindene moiety. Methods for adding the crystal control compounds (1) to (V) include a method in which they are added in advance to a protective colloid solution, a method in which they are added gradually as silver halide grains grow, and a method in which these are added in combination. In the method for producing silver halide grains according to the present invention, grains may be grown by using seed grains and growing phosphorus halide on their surfaces. In the method for producing silver halide grains according to the present invention, the step of producing silver halide to form halide ff1 grains is carried out at t3 in the presence of 7 ammonium 7, and double-noeting an ammoniacal silver nitrate aqueous solution and a halide aqueous solution. Preferably, it is added by a method. Further, in this particle r&dispersion process, it is preferable to add a silver and halide solution so that new crystal nuclei are not generated. The feature of this manufacturing method is that it can provide a silver halide emulsion with excellent monodispersity, as described in VF Bunsho No. 61-83531. The outline of the method for producing silver halide grains having (331) planes according to the present invention has been described above.
You can know this from book No. 1-83531 #I. The silver halide grains having (331) planes according to the present invention are produced by cadmium salts, zinc salts, lead salts, thallium salts, ilinium salts or their complex salts, rhodium salts or their complex salts, in the process of silver halide grain formation or physical ripening. complex salt,
Iron salts or complex salts thereof, gold salts or complex salts thereof, etc. may also be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used. sulfonic acid) or gelatin conductor (eg, acylated gelatin, carbamoylated gelatin, etc.) using a precipitation method (70 curage run method). Silver halide grains according to the invention are chemically sensitized. The conditions of the chemical ripening or chemical sensitization process, such as pH, C
There are no particular restrictions on IAIF, temperature, time, additives, etc., and it can be carried out under conditions commonly used in the industry. For chemical sensitization, sulfur sensitization method uses sulfur-containing compounds that can react with silver ions or active gelatin, selenium sensitization method uses selenium compounds, reduction sensitization method uses reducing substances, gold and other A noble metal sensitization method using a noble metal compound can be used alone or in combination. As the sulfur sensitizer, known ones can be used.
Examples include thiosulfate, allylthiolupamide, thiourea, allyl isothiocyanate, cystine, 9-)luenethiosulfonate, logenine, and the like. Others, U.S. Pat. No. 1,574. No. 944, No. 2.411), No. 689, No. 2,278,
No. 947, No. 2,728゜668, No. 3,501.3
No. 13, No. 3, No. 656, No. 955, West German Survey Publication (
OLS) No. 1,422,869, JP-A-58-249
Sulfur sensitizers described in No. 37, No. 55-45016, etc. can also be used. The amount of yellow sensitizer added is
The amount may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as the amount of nitrogen-containing bicyclic compound added, pl+, temperature, and the size of silver halide grains, but as a guide, it is approximately 10% per mole of ia halide. -1 mol to about to-' mol is preferred. Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic mole/cyanates such as allyl isoselenocyanate, selenoureas, selenoketones, mole/amides, etc. selenocarboxylic acids and esters, selenophosphates, diethylselenide, selenides such as diethylselenide, and the like can be used, and specific examples thereof can be found in US Pat.
No. 574,944, No. 1,602,592, No. 1,6
23.499. As with the sulfur sensitizer, the amount added varies over a wide range, but as a guide, approximately 10-
The amount is preferably about 1 mol to 10 −1 mol. In the present invention, as the gold sensitizer, various gold compounds can be used, whether the gold has a valence of +1 or +3. Typical examples include chloraurate, potassium chloroaurate,
Auric Trichlorai Y. Potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is about 10-7 to 10-7 mol per mol of silver halide.
Ranges up to 'molar are preferred. Preferred compounds that release gold ions from gold-gelatinate and promote ion-containing adsorption onto silver halide grains include R2MX and R3M'X. or M'X, (wherein R represents a hydrogen atom, ammonium group, or alkali metal atom, M represents pt or Pd,
M′ represents Ir or Rb, and X represents a halogen atom) Rh%Pd, Ir, pt￥
? complex salts are effective. Specific compounds include (NH4)zPLcL, (old +,
), PdCf4, 31rBrss (old 1.), R
hCe6-1211.0, etc., but particularly preferred is ammonium tetrachloropalladate (II) (
NIl, ), PdC14. The amount added is 10 to 10 in stoichiometric ratio (mole ratio) to the gold sensitizer.
A range of 100 times is preferred. The timing of addition may be at the start of chemical ripening, during ripening, or after the end of ripening, but preferably during chemical ripening, and particularly preferably at the same time as or before or after the addition of the gold sensitizer. In the present invention, reduction sensitization can also be used in combination. There are no particular limitations on the reducing agent, but known examples include stannous chloride, urea dioxide, hydranone derivatives, and polyamines. Reduction sensitization is performed during rR sensitization of halogenated 11 particles, but chalcodene sensitization, gold sensitization, Rh, Pd,
It is preferable to carry out the sensitization after completion of sensitization with a compound selected from noble metal compounds such as Ir and pt. The core/shell type silver halide grains in the present invention have a grain structure composed of at least two layers having different silver iodide contents, and the silver iodide content is present on the grain surface of the two or more layers. It is preferable that the rate is lower than that inside. In the above-mentioned core/shell type silver halide grains, the gradient due to the difference in content from a layer with a high silver iodide content to a layer with a low silver iodide content may have a sharp boundary, and the boundary may not necessarily be It may be something that changes continuously and is not obvious. In addition, an internal high silver iodide type core/shell emulsion consisting of a plurality of nitrogen atoms as described in Japanese Patent Application No. 60-86659 is preferable, and the core is a part of the emulsion (for example, a part corresponding to a seed grain in production). There is no problem even if the silver iodide content is small or there is an O part, and the thickness of the shell is such that it does not hide the favorable qualities of the core, and conversely, the unfavorable effects and qualities of the core are suppressed. It is preferable that the thickness is sufficient to hide it. The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can also be investigated by measuring luminescence at low temperatures. The silver halide emulsion having the above-mentioned core/shell type silver halide grains is preferably manufactured by forming a monodisperse silver halide grain into a core by coating the core with a shell. In order to produce the monodisperse silver halide grains of F7 above, grains of a desired size can be obtained by the gupurujet method while keeping the pAg constant. For example, the monodisperse silver halide emulsion is For example, a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing halide ffi seed particles. Produced by a method of varying rate of addition over time as a function of particle surface area. At this time, highly monodisperse silver halide grains can be obtained by appropriately selecting the time function of addition rate, pH, pAg, temperature, etc. Regarding the method for producing the above-mentioned core/shell type silver halide grains, for example, West German Patent No. 1,169,290, British Patent No. 1,027,146, and Japanese Patent Application Laid-open No. 154232/1989
Reference can be made to the descriptions in Japanese Patent Publication No. 51-1417, etc. The silver halide grains according to the present invention can be optically sensitized to a desired wavelength range. The optical sensitization method is not particularly limited, and for example, an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a tumetine dye, or a trinotine dye or an optical sensitizer such as a merocyanine dye is used alone or in combination (for example, supersensitization). Can be optically sensitized. Regarding these technologies, see U.S. Patent No. 2,688.545, U.S. Pat.
No. 3,615.635, No. 3,828°964, British Patent No. 1,195,302, No. 1,242.588, No. 1,293.862, West German Patent (OLS) 2,
No. 030,326, No. 2,121.780, Special Publication No. 4
It is also described in No. 3-4936, No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the light-sensitive material.6 Silver halide of the silver halide emulsion layer containing silver halide grains according to the present invention. The emulsion may contain various compounds at the end of chemical ripening for the purpose of preventing the occurrence of X during its manufacturing process, storage or development, or for stabilizing photographic performance. For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, etc. 7zoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole, etc.); also mercapto and liminones, mercaptotrianones, thioketo compounds such as oxazolinthione, and also benzenethiosulfinic acid, benzenesulfinic acid, Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides, hydroquinone derivatives, 7-mi/7-ethanol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. These compounds It is preferable to add it during chemical ripening or before coating.As the gelatin contained as a binder in the silver halide emulsion layer of the present invention, ordinary photographic gelatin is preferable.
Not only gelatin but also derivative gelatin is included, and derivative gelatin includes reaction products with gelatin acid anhydride,
Included are reaction products between gelatin and isocyanate, or reaction products between gelatin and a compound having an active halogen atom. The acid anhydrides used in the reaction with gelatin include, for example, maleic anhydride, 7-talic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, etc., and the incyanate compounds include: For example phenyl isocyanate, p-bromophenylisonanate, p-chlorophenylisocyanate), p-)
Examples include lylisocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having active halogen atoms include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-7e/xybenzenesulfonyl chloride, p7'lomobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, Benzenesulfonyl chlorite, p-sulfobenzoylnochlorite, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-
2) O-4-7 minobenzenesulfonyl chloride, 2
-carboxy-4-bromobenzenesulfonyl chloride, -carpoquinbenzenesulfonyl chloride, 2
-ami/-5-methylbenzenesulfonyl chloride,
7thalyl chloride, p-nitrobenzoyl chloride, penzoyl chloride, ethyl chlorocarbonate,
70yl chloride and the like are included. As a binder for the silver halide emulsion layer of the present invention, hydrophilic colloids other than gelatin, such as colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl content of 19 to 2, within a range that does not impair the effects of the present invention.
Cellulose derivatives such as cellulose acetate hydrolyzed to 6%, polyacrylamide, imidized polyacryl 7mide, casein, e.g. vinyl alcohol-
Vinyl alcohol polymers containing urethane carboxylic acid groups or shea/7 cetyl groups such as vinyl shea/acetate copolymers, polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymerization of proteins or saturated acylated proteins with vinyl group-containing The resulting polymer, polyvinylbilinone, polyvinylamine,
Polyamide/ethyl methacrylate, polyethyleneimine, etc. can also be used. The gelatin hardener used in the silver halide emulsion layer of the present invention reacts with gelatin to form a 9A bridge and generates an organic or inorganic acid as a by-product when exhibiting a hardening effect. Examples include 2,3-noherode/malaldehyde acids that release hydrohalic acids (U.S. Pat. No. 2,080,01
No. 9), 2,4-fuchloroS-trifunone (U.S. Patent 3,362゜8
No. 27, West German Patent Publication 1ml, No. 921,363), Fukuro 0 Phosphoamide Derivative (British Patent No. 974.7)
23, 1,004, 658), halomethyl derivatives (British Patent No. 990°275), 7-male 7-onitrile chloride derivatives (US Pat. No. 3,186,848),
Alternatively, derivatives of 2-7dinoxy-3-halodenormalaldehyde acids releasing carbolic acid derivatives (UK Patent No. 1,19
No. 2,775), and particularly preferred are compounds represented by the following general formula (Vl). The blank space below represents the general formula (Vl) N where 1 represents an alkali metal atom. These gelatin hardeners can be mixed with water, methanol, trimethylformamide, or water, dissolved in a solvent that does not harm the photographic emulsion, and added at any stage before coating the emulsion. . These hardeners are preferably used in an amount of 1-1 to 1-2 dry weight of gelatin in the gelatin-containing coating solution.
00. An appropriate hardening effect can be provided by adding a certain amount, and the optimum amount is in the range of 5 to 60 g. Specific examples of the above-mentioned hardening agents include the following. Ca) C/-C-COOI+C! -C-CI
IO (1+) Br112Cco N11-CI! 2-
CI! 2Nil-COCll□Dr In the silver halide emulsion layer of the present invention, other hardeners may be used in combination with the above-mentioned hardener to the extent that the effects of the present invention are not impaired. Other hardening agents include aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, derivative compounds thereof such as 7-cetal or sodium bisulfite adducts, methanesulfonic acid ester compounds, epoxy compounds, and aziridine. type compounds, maleic acid imide type compounds, active vinyl type compounds, carboimide type compounds, inoxazole type compounds, N
-Notyrol compounds, incyanate compounds, chromium alum, zirconium sulfate, etc. 5! [Hardening agents can be mentioned.] The silver halide emulsion layer of the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic properties improvement (
For example, various known surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization. That is, U.S. Patent Nos. 2,240.472 and 2,83
No. 1,768, No. 3,158.484, No. 3,210
, No. 191, 3, 294. No. 540, No. 3,507,860, British Patent No. 1,01
No. 2,495, No. 1,022,878, No. 1,179
, No. 290, No. 1,198,450, U.S. Patent No. 2,7
39.891, 2,823,123, 1,17
9゜290, 1,198.450, 2,739
．． No. 891, No. 2,823゜123, No. 3,068.
No. 101, No. 3,415,649, No. 3,866゜4
No. 78, No. 3,756,828, British Patent No. 1,397
．． No. 218, No. 3,113,816, No. 3,411.
No. 413, No. 3,473.174, No. 3,345.9
No. 74, No. 3,726,683, No. 3,843.36
No. 8, Belly Patent No. 731,126, British Patent No. 1,1
38.514, 1,159,825, 1,37
No. 4,780, U.S. Patent No. 2,271゜623, No. 2,
No. 288.226, No. 2,944,900, No. 3,2
35゜919, 3,671,247, 3,77
No. 2,012, No. 3,589゜906, No. 3,686
．． No. 478, No. 3,754,924, West German Application Publication (
OLS) No. 1,961,683 and Japanese Unexamined Patent Publication No. 1983-11
No. 7414, No. 50-59025, Special Publication No. 40-37
8, No. 40-379, and No. 43.13822, such as saponin (steroid P), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol furkyl or furkylar). - ethers, polyethylene glyfur esters, polyethylene glyfur sorbitan esters, polyalkylene glycol furkylamines or amides, polyethylene oxide adducts of silicone)
, glycidol derivatives (e.g. flukenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, furkyl esters of sugars, nonionic surfactants such as urethane necks or ethers, triterbemade saponins, Furkyl carboxylate, 7-rukylbenzenesulfonyl sulfate, furkyl phosphate ester, N-7silu-N
- Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphorus, such as furkyltaurines, sulfosuccinates, sulfofurkyl polyoxyethylene furkylphenyl ethers, polyoxyethylene furkyl phosphates, etc. Anionic surfactants containing acidic groups such as acid ester groups, amphoteric surfactants such as amylpHM, 7-minofurkylsulfonic acids, aminoalkyl sulfates or phosphoric acid esters, furkyl betaines, amine imides, and amine oxides. , furkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic tjS quaternary ammonium salts such as pyridium, imidazolium, and sulfonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. . In the silver halide emulsion layer of the present invention, as a development accelerator,
In addition to the surfactants mentioned above, OLS 2,
No. 002,871, No. 2,445,611, No. 2,3
It may also contain imidazoles, thioethers, selenoethers, etc., which are described in No. 60,878 and British Patent No. 1,352.196. In addition, in order to apply the present invention to a color photographic material, a combination of cyan, magenta and yellow couplers may be contained in each red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer according to the present invention. The method and materials used for photosensitive materials may be used; it is desirable that the coupler has a hydrophobic group called a ballast group in its molecule and is non-diffusive.
It may be either equivalence, or it may contain a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (so-called DIR coupler). A coupler such as . As the yellow coloring coupler, a known IJ1111 ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are U.S. Pat.
No. 506, No. 3,408,194, No. 3,551,1
No. 55, No. 3゜582.322, No. 3,725,07
No. 2, No. 3,891,445, West German Patent No. 1,547,
No. 868, West German Publication (OLS) 2,213°46
No. 1, No. 2,219.917, No. 2.261,361
No. 2,414°006, No. 2,263,875, etc. As the magenta color-forming coupler, pyrazolone compounds, ingzolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat.
No. 00,788, No. 2,983,608, No. 3,06
No. 2,653, No. 3,127,269, No. 39314
．． No. 476, No. 3,419,391, No. 3,519,
No. 429, No. 3,558.319, No. 3,582.3
No. 22, No. 3,615.506, No. 3,834゜90
8 No. 3,891,445, West German Patent No. 1,810.46
No. 4, West German IEI Public II (QLS) 2-46
8,665+, 2,417.945, 2,418
, No. 959, No. 2,424,467, Special Publication No. 1977-6
This is described in No. 031, etc. As cyan coloring couplers, phenolic compounds, Kabutol thread compounds, etc. can be used. Specific examples include U.S. Patent Nos. 2,369,929 and 2,4.
No. 34,272, No. 2,474,293, No. 2,52
No. 1.908, No. 2,895.826, No. 3,034
, No. 892, No. 3.3LL, No. 476, No. 3, 458
No. 1315, No. 3,476.563, No. 3,583.
No. 971, No. 3,591゜383, No. 3,767.4
11%, [Publication of L Application (OLS) 2゜414, 83
No. 0, No. 2,454,329, JP-A-4111-59
This is described in No. 838, etc. As a colored coupler, for example, U.S. Patent No. 3.476゜5
No. 60, No. 2,521,908, No. 3,034,89
No. 2, Japanese Patent Publication No. 44-2016, Japanese Patent Publication No. 38-22335, Japanese Patent Publication No. 42-11304, Japanese Patent Application No. 44-32461, Japanese Patent Application No. 49-98469, Japanese Patent Application No. 50-118029, West German Publication (OLS) 2. 418.959 can be used. [) As the IR cover, for example, U.S. Pat. No. 3,227.554, U.S. Pat.
No. 83, No. 3,790°384, No. 3,632,34
No. 5, OLS No. 2.414,006,
Those described in Japanese Patent No. 2,454,301, Japanese Patent No. 2,454,329, British Patent No. 953,454, and Japanese Patent Application No. 146,570/1988 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, U.S. Pat.
No. 2,417,914 can be used. Other Tokuko Showa 55-8554
No. 9, No. 5 Hu 94752, No. 56-65134,
No. 5B-135841, No. 54-130716, No. 56-133734, No. 56-135841, U.S. Patent No. 4.310.618, British Patent No. 2,083,64
No. 0, Research Disclosure 18360 (19
79), 14850 (1980), 19033
(1980), 19146 (1980), 205
25 (19th year), 21728 (1982) can also be used. Two or more of the above couplers may be contained in the same layer. Further, the same compound may be contained in two or more different layers. To introduce the coupler into the silver halide emulsion layer, known methods such as those described in U.S. Pat. No. 2,322,027 can be used.
phosphoric acid esters (diphenylphos 7z-),) liphenyl phosphate 7ate, trifrenol phosphate, nooctyl 7-thale), citric acid esters (e.g. 7-cetyl tributyl citrate) , benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. dienal laurylamide), etc., or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, enal propionate. ,
Secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl alkylene acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent may be mixed with a low boiling point organic solvent. When Kabra has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally added in an amount of 2.times.10@-' moles to 5.times.10@-' moles, preferably 1.times.10@-2 to 5.times.10@-' moles per mole of silver in the silver dendenide emulsion layer. The light-sensitive material according to the present invention may contain a hydroquinone derivative, an ami/phenol conductor, a gallic acid derivative, a 7-scorbic acid derivative, etc. as a color cast preventive agent (specific examples thereof can be found in U.S. Pat. No. 2,360,290). No. 2, 3
36, 327, No. 2,403,721, No. 2,41
No. 8,613, No. 2,675,314, No. 2,701,
No. 197, No. 2,704,713, No. 2, 728
, No. 659, No. 2,732,300, No. 2.735
．． No. 765, JP-A No. 50,92988, JP-A No. 50-92
No. 989, No. 50-93928, No. 50-11033
No. 7, Japanese Patent Publication No. 50-23813, etc. 4i'! Effective antistatic agents include noacetylcellulose, styrene-perfluoroalkylsonium maleate-F copolymer, and alkali salts of reaction products of styrene-maleic anhydride copolymer and 9-7 minobenzenesulfonic acid. It is. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. The latex added to improve the physical properties of the film may include a copolymer of acrylic acid ester, vinyl ester W, and a monomer having an ethylene group (t). Examples of the gelatin plasticizer include glycerin and glyfur compounds, and examples of the binder include styrene-sodium maleate copolymer, alkyl vinyl ether-maleic a co-m6, and the like. Supports for the photosensitive material according to the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, etc.
There are polystyrene and the like, and these supports are appropriately selected depending on the intended use of each photosensitive material. These supports are subjected to undercoat processing if necessary. After exposure, the photosensitive material according to the present invention can be developed by a commonly used known method. The black and white developer is hydroquinebenzene, Ami77E/-
It is an alkaline solution containing developing agents such as metals, aminos/benzenes, and other alkali metal salts such as sulfites, carbonates,
May include bisulfites, bromides and iodides. Further, when the light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal method, the image is first developed with a black-and-white developer, then exposed to white light or treated with a bath containing a capri agent, and then color developed with an alkaline developer containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied.
For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and stabilization treatment if necessary, or a method in which bleaching and fixing are separated after color development. If necessary, a method of further washing with water and stabilizing treatment can be applied. The photosensitive material according to the present invention can be applied to many uses, such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching method, reversal use, diffusion transfer method use, etc. It can be used for Further, when applied to multilayer color light-sensitive materials, the present invention can be applied to various layer configurations well known in the art, ie, normal layer, reverse layer, and any NJ configuration. rExample] The present invention will be specifically described below with reference to Examples. Example 1 Comparative octahedral silver iodobromide emulsions EM-1 and silver iodobromide 7L polished EM-2 having a (3:11) plane, and a core having a (331) plane of the present invention were prepared by the following method. / Shell type iodobromide 1a? lJllEM-3wo3sl L m. (EM-1) Monodispersed 8 by the method described in JP-A-60-145440
A hedral silver iodobromide emulsion was prepared. That is, gelatin and 4-hydroquine-6-7thyl-1.3.3 at 40°C.
a. In the presence of 7-chitrazaindene, a mixed aqueous solution of ammoniacal silver nitrate and potassium bromide potassium iodide was added to a solution containing 0.15 micron grains of silver iodide seed (silver iodide content: 4 mol%). It was manufactured by adding using a controlled dog pull jet method, requiring a minimum amount of time without generating small particles. During this addition, I) Ag was changed continuously from 9 to 10. The molar ratio of potassium iodide to added silver nitrate was 8%. Next, after desalting by a conventional method, gelatin was added and redissolved. As a result of electron microscopic observation, EM-1 contained almost perfect octahedral grains consisting of (111) crystal faces. (EM-2> Silver iodobromide grains with an average grain size of 0.40μ (silver iodide content 4
The emulsion containing 0.29 mol (mol%) was added to 1000 ml of distilled water.
4-hydroxy-6-methyl-1,3,3m,7-
In the presence of citrazaindene, at 50°C 1:0.
A mixed aqueous solution of 47 mol/l silver nitrate aqueous solution filooomZ and necessary and sufficient potassium bromide and potassium iodide! (8 mol%
(containing potassium iodide) was produced by a controlled double jet method according to the method described in JP-A-61-83531. Next, after desalting by a conventional method, gelatin was added and redissolved. As a result of electron microscopy TFT observation, EM-2 is (:+
31) It contained an almost perfect icosahedron consisting of crystal planes. (EM-3) Next, the core/shell emulsion of the present invention was prepared in JP-A-61-8823.
Average particle size 0°40 manufactured according to the method shown in No. 5
An emulsion containing 0.29 mol of μ-octahedral silver bromide grains (1000 ml of distilled water, 1000% ammonia (containing 30 ml))
4-hydroxy-6-methyl-1,
In the presence of 3,3a17-chitrazaindene, 500 liters of a 0.47 mol/l silver nitrate aqueous solution and the necessary mixed aqueous solution of potassium bromide and potassium iodide (containing 15 mol% potassium iodide) at 50°C. was added by controlled double jet method, followed by addition of 0.47 mol/l.
Aqueous solution of silver nitrate 9500I61 and the necessary potassium bromide and potassium iodide mixed water? 8 liquid (containing 2 mol % potassium iodide) was added by the Funtrorugpurnoet method. Next, after desalting in a conventional manner, gelatin was added and redissolved. EM-3 created in this way is a core/shell emulsion with a high iodine shell inside, and as a result of electron microscopy observation, it has an almost perfect rhombic shape consisting of (:+31) crystal planes.
It contained facepiece particles. Chemical sensitization was applied to each of the above EM-1 to EM-3 in accordance with a conventional method, and the sensitizing dye (as described below) was added at 1,5X IF5 and 1,OX, respectively, per mole of silver halide.
Spectral sensitization to green sensitivity was achieved by adding 10-S mol. These emulsions contain 4-hydroxy-6-methyl-1°3.
3a,7-thitrazaindene at 9,4X 10-' mole per mole of silver halide and 1-phenyl-5-mercaptetrazole at J! 1.6 per mole of t
It was stabilized by adding 10-4 mol. Each sample was coated with the following layers on a subbed cellulose triacetate support so that the silver amount was 15 TofI/d+o''.The amounts of components in the description of each layer of the sample indicate the amounts per 1 m2. 1st layer: 1.8 g of the above halogenated kite milk, 0.20 g of the following magenta coupler MB-1, and 0.04!h of the following colored magenta coupler CM-1 were subjected to i8M. (1,06
, a high-sensitivity green-sensitive emulsion layer containing a DNI' (Notan Yary/Nil 7 E/L) dispersion. ff≦2 (ri: 0, 15g of yellow colloidal silver, 0.2y of anti-fouling layer dissolved. Yellow filter layer containing TIy of DIIP (butyl terephthalate) dispersion and 1.52g of gelatin. B-1 I M-1 Cσ Ct' In addition to the above additives, hardening agents H1 and 112 below were added to the above No. 1 NJ and No. 271 as shown in Table 1. The amount of 111 added was 8-g per 1 g of gelatin. , +12 is 12B. l basket 1 [(C112= CH30□CH2)3CC112SO
□CLCLI□NCHaCHzSOJ Each sample was subjected to wedge exposure according to a conventional method and processed through the following processing steps. For the measurement of heat fog, the sample was heated to 65°C before wedge exposure.
It was stored for 3 days under conditions of 1 relative temperature and 20%. Processing steps: Color development, bleaching for 3 minutes and 15 seconds, washing with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below. Color developer 4-7 Minnow 3-methyl-N-(β-hydroxyethyl)-aniline sulfate 4.75° Anhydrous sodium sulfite 4,259 Hydroxylamine 1/2 sulfate 2.02 Anhydrous potassium carbonate
37.5゜Potassium Bromide
1.3g nitrilotriacetic acid trisodium salt (1
Water salt) 2.52 Potassium hydroxide Add t, og water to make 11. Bleach solution ethylenenoamine titraacetic acid iron ammonium salt 100.
09 Ethylenenoamine chitra vinegar PI12 ammonium salt 10
．． 0g Ammonium bromide 150.0g Hydroxylic acid 10. The pH was adjusted to 11 by adding O+aZ water, and the pH was adjusted to 6.0 using ammonia water. Fixer Ammonium thiosulfate 175.0g Anhydrous ammonium sulfite 8.697 Sodium sulfite 2.3g Water was added to make li, and acetic acid was used to prepare 1 layer of pl(6,0). Stabilizing liquid k v 'J (37% aqueous solution) 1.
5@1 Konidafukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.
5+1 Add water to make 11. The developed samples were tested for sensitivity and
) was measured. Sensitivity is the sensitivity at the point of Capri +0.1 on the characteristic curve,
The sensitivity is expressed as a relative value with the sensitivity of sample No. 1 as 100. The results are shown in Table 1. In Table 1, thermal fog: (JS' for the sample subjected to the above-mentioned high-temperature preservation) - (fogging for the sample not subjected to the above-mentioned high-temperature preservation). One hundred++. Table 1 As is clear from Table 1, the samples according to the present invention have a higher degree of heat generation and less heat fog than the comparative samples. Example 2 The EM-L to εM-3 were subjected to chemical sensitization according to a conventional method,
A color photosensitive material consisting of 11 layers having three types of photosensitive layers: a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer was prepared in the following manner. EM-1 to EM- subjected to chemical sensitization
Emulsion No. 3 was changed only in the green-sensitive high-speed layer (fifth layer). All of the other photosensitive layers in each sample were the same (a common emulsion was used). A multilayer color photosensitive material consisting of each layer of the following composition was prepared on a subbed cellulose triacetate film support. Pt51 Layer: Antihalation layer Gelatin layer containing black colloidal silver.Second scrap: Intermediate layer gelatin layer containing an emulsified dispersion of 2.5-L-octylhydroquinone.Third layer: Low-sensitivity red-sensitive silver halide emulsion layer average Particle size (i
)0.30μ, 8gl 6mol% Δg[1r
Monodispersed emulsion (emulsion...silver coating amount) consisting of
1.897m2 Sensitizing dye!・・・・・・6X 1 for 1 mole of silver
0-'molar increase in color cord■ ・・・・・・／＃
1.0X10-'Morsian coupler (C-1)・
... 0.06 mol per mol of silver Colored cyankabra (CC-1) 0.003 mol DIR compound (D-1) per 1 mol of silver ... Silver II! ! 0.0015 mol (D-2)・
... 0.002 mol per mol of silver fi4 layer: high sensitivity red-sensitive silver halide emulsion layer average grain size (
”) 0.5μm, 8gUr containing 8917.0 mol%
Monodispersed emulsion (emulsion ■) consisting of L... Silver coating Jl 1.
3y/m" Sensitizing dye I...3X 10-' mol per 1 mol of silver■...
1. OX 10” Morcian coupler (C-1)...
... 0.03 mol per mol of silver 1) IR compound ([1-2) ... o-ooi mol per mol of silver 5th layer: Intermediate layer ((, L, ) Gelatin layer same as 2nd layer. 16th layer: Low sensitivity green sensitive silver halide?LM layer milking I
...Amount of coated silver 1.5g/m" Sensitizing dye ■...!2.5X 1 per mole of Il
0-'mol ■・・・・・・ 1.2
X 10-5 mole magenta coupler (M[1-1)...
...0.045 mol colored magenta coupler (CM-1) for 1 mol of silver...1 silver
Per mole 0.009 mol [1[R compound (El-1)...... per 1 mol of silver 0.0010 mol (D-3)...... per 1 mol of silver Q, QQ30 mol FA7 layer: high sensitivity green sensitive silver halide emulsion layer emulsion (EN
-1-EM-3) --- Silver coating i1 1,4y/
m” sensitizing dye ■・・・・・・1.5 per mole of silver
X 10-'mol ■・・・・・・ 1
．． OX 10-'Mor Magenta Cabra (M[1-1)・
...0.030 mol DIR compound (D-3) per 1 mol of silver... s O,
0010 mol 8th layer: yellow filter layer yellow colloidal silver and 2.5-note t-octylhydride r:
A gelatin layer comprising an emulsified dispersion of I/Kin. 9th M: Low-speed blue-sensitive silver halide emulsion layer average grain size 0.
48 μs, monodispersed emulsion (emulsion ■) consisting of 828 liters containing 6 mol% of Apl... Silver coating amount
0.9y/+o” Sensitizing dye V...1.:lX per mole of silver
10-' mole yellow coupler (Y-1)...
0.29 mol per mol of silver 10th wJ: High sensitivity blue-sensitive emulsion layer average grain size 0.8 μI, containing 115 mol % of Br
Monodispersed emulsion (emulsion ■) consisting of 1. Silver coating amount 0.597 x 2 Sensitizing dye ■...1. OX
10-' mol Yellow coupler (Y-1)...0.08 mol per 1 mol of silver DIR compound (D-2)... 0.0
15 mol 11th layer: 1st protective layer iodine m<N1 mol%, average particle size 0.07 μm) Silver coating fl O, 59/Ugly 2 UV absorber uv-
1. Gelatin layer containing UV-2. 1st UI: second protective layer gelatin layer containing polymethyl acrylate particles (diameter 1.5μ) and formalin scavenger (IIS-1>).In addition to the above composition, each layer also contains a gelatin hardener (1.5 μm in diameter). !1
or 112) and a surfactant were added. Gelatin hardener H1 contains 8aAg per gram of gelatin, t
In the case of 12, 12IIg was added. Sensitizing dye I: Anhydro 5.5'-Fucloro 9-
Ethyl-3,3'-no(3-sulfopropyl)thiacarposi7ine hydroxide sensitizing dye '−
Nobenzothiacarpocyanine hydroxide ■: Anhydro 5,5'-nophenyl-9-ethyl-
3,3'-no(3-sulfopropyl)oxacarbocyanine hydroxide■: Anhydro9-3,3'-no(3-sulfopropyl)-5,6,5',6'-dibenzoxacarbocyanine hydroxide 7-hydro-3,3'-no(3-sulfopropyl)
-4,5-benzo-5'-methoxythiacyanine Below margin C-1: n CC-1: 0 (I Y-1: I uv-i: 11V-2: Its-1: , n I D- 1=nl+D-2=D-3: The thus produced multilayer color speculative material was stored at a high temperature for measurement of heat in the same manner as in Example 1, and a white wedge was prepared according to a conventional method. The sensitivity, brightness, and thermal brightness were measured using green light in the same manner as in Example 1. The results are shown in Table 2. It can also be seen that the sample according to the present invention has higher sensitivity and less thermal fog than the comparative sample. Thermal fog and multilayer desensitization of the silver halide photographic light-sensitive material are improved. Therefore, the silver halide photographic light-sensitive material according to the present invention has high sensitivity and low heat fog.

Claims (1)

[Claims] At least the grain surface consists essentially of silver bromide or silver iodobromide, has a (331) crystal plane on the outer surface, and has a core/shell structure with a higher silver iodide content inside than the grain surface. A halogen containing silver particles and at least one silver halide emulsion layer containing gelatin as a binder and hardened with an organic hardener that reacts with the gelatin to release an organic or inorganic acid. Silver chemical photographic material.