JPH0584507B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material. In particular, a novel method for preparing silver halide emulsions and
The present invention relates to a method for producing a silver halide photographic material containing a silver halide emulsion prepared by a novel method. (Prior Art) In the production process of silver halide emulsions (particularly the precipitation process and physical ripening process), compounds that are adsorbed onto the surfaces of silver halide crystal grains are often added. For example, in silver halide photosensitive materials that require high resolution (e.g., emulsions for IC dry plates), it is necessary to make the grain size of silver halide crystals smaller, and to reduce the large grains that tend to occur during the precipitation process. A compound that adsorbs to silver halide is added to prevent the formation of (giant grains). Furthermore, in recent years, so-called bright-room photosensitive materials, which can be handled even under bright indoor lights, have been widely used in silver halide photosensitive materials for printing purposes in order to improve the working environment. In order to prevent the increase in fog, sensitive materials based on silver chloride are made, but in order to have sufficient density,
It is necessary to add a compound that adsorbs to silver halide in order to make the grains finer and prevent the generation of giant grains. In order to obtain a so-called monodisperse silver halide emulsion with uniform grain size, it is necessary to use the so-called controlled double jet (CDJ) method in which silver ion concentration is maintained constant. However, the presence of even a small amount of these compounds adsorbed on silver halide generally significantly suppresses the formation of twins, and makes it possible to easily form monodisperse silver halide emulsions even in a halogen-rich atmosphere with a considerably high pAg. Therefore, a monodisperse silver halide emulsion can be easily obtained without using the CDJ method.
Of course, if the CDJ method is used, a silver halide emulsion with better monodispersity can be obtained. Furthermore, the “Journal of Photographic Science”
Photographic Science) Vol. 21, p. 39, 1973, as is known from Japanese Patent Publication No. 55-42737, a unique crystal habit [(111) plane (octahedron) or ( 110) Silver halide grains with faceted silver chloride and silver chlorobromide crystals can also be produced in some cases by adding compounds that adsorb to these silver halides. Also, in silver bromide or silver iodobromide crystals,
If mercapto is added during grain growth and the silver ion concentration is kept at a certain value, (110) planes can be obtained in addition to the (100) and (111) planes obtained by the normal CDJ method.
It is also possible to obtain crystals with a faceted surface (rhombidodecahedron). Chemical ripening of silver halide emulsions (e.g.
When performing sulfur sensitization, noble metal sulfur sensitization, etc.
When chemical ripening is performed in the presence of compounds that adsorb to silver halide, chemical sensitization is generally suppressed, but under certain conditions, such as when the amount of sensitizer is increased, the gradation becomes sharper, although the relative sensitivity is lower. Benefits such as this may be obtained. However, these compounds adsorbed on silver halide are also compounds generally called antifoggants or stabilizers, so when silver halide emulsion grains are prepared in the presence of these compounds, they remain in the emulsion even after washing with water. If this is done, the subsequent chemical ripening by chemical sensitizers will be significantly inhibited, and development will also be inhibited, resulting in a significant decrease in photographic density and photographic sensitivity, making it extremely difficult to use. There are some problems. Furthermore, if these are forced to coexist during chemical ripening, there is a problem in that even though fog and gradation are improved, sensitivity is significantly lowered. Furthermore, there is also the problem that adsorption of spectral sensitizing dyes to silver halide grains is significantly inhibited. For this reason, it is necessary to remove or deactivate compounds adsorbed to silver halide used in emulsion production before coating. (Problem to be solved by the invention) There is a European patent for a method for deactivating sulfur-containing inhibitors such as mercapto compounds.
There is a method using an oxidizing agent as disclosed in 144990A ₂ . This invention makes it possible to produce silver halide grains using compounds that could not be used until now due to the problems described above. However, especially in the production of highly sensitive silver halide grains, there were still some unsatisfactory points, such as an emulsion with lower sensitivity than expected, probably due to the side effects of the oxidizing agent. Therefore, a method other than this to deactivate or remove compounds adsorbed on silver halide has been desired. On the other hand, development is known in which unexposed areas of a silver halide photographic light-sensitive material undergo undesirable changes in density after development. In the case of negative-working silver halide photosensitive materials, the density of unexposed areas increases, which is called "fog." Furthermore, in the case of positive-working silver halide photosensitive materials, this appears as a decrease in maximum density. (Hereinafter, for simplicity, both phenomena will be referred to as "fogging".) This phenomenon is
Normally, this problem is more likely to occur when a highly sensitive photosensitive material is manufactured, and the longer the storage period between manufacturing and use of the photosensitive material, and the higher the temperature and humidity of the storage atmosphere, the more likely it is to occur. The occurrence of fog deteriorates the S/N ratio of the silver halide photographic light-sensitive material used as an image recording material, which is undesirable. As a method for preventing the occurrence of fog in silver halide photographic light-sensitive materials, a method is conventionally known in which a compound called an "antifoggant" is incorporated into the light-sensitive material. Antifoggants include mercapto compounds represented by mercaptotetrazoles and mercaptotriazoles, heterocyclic compounds such as benztriazoles, benzimidazoles, tetraazaindenes, and triazaindenes;
Inorganic compounds such as oxides of basic metal salts, phenol derivatives such as gallic acid, and a large number of other compounds are already known. However, these compounds are unsatisfactory to those skilled in the art because they either cause a significant decrease in sensitivity or have insufficient antifogging ability when added in amounts greater than the effective amount as antifoggants. It was hot. For example, 1-phenyl-5-mercaptotetrazole, which is one of the famous antifoggants, has a high antifogging ability, but has a very large decrease in sensitivity. In addition, the 1-phenyl-5-mercaptotetrazole derivative in which two carboxyl groups are substituted for the phenyl group described in U.S. Patent No. 3,266,897 is
Compared to 1-phenyl-5-mercaptotetrazole, the decrease in sensitivity is significantly reduced, but the antifogging ability and
In particular, the ability to suppress fogging of photosensitive materials stored under high temperature and high humidity conditions is insufficient. For these reasons, there is a limit to the function of antifoggants, and there has been a desire for a silver halide that does not easily cause fogging even without such additives. An object of the present invention is to provide a method for producing a silver halide photographic material comprising a silver halide emulsion, which solves the above-mentioned problems that occur when a compound adsorbed on the surface of silver halide grains is used. Another object of the present invention is to suppress the effects of compounds adsorbed on silver halide used in the production process of silver halide emulsions, thereby making it possible to perform appropriate chemical ripening, spectral sensitization, etc. An object of the present invention is to provide a method for producing a photographic material comprising an emulsion. Another object of the present invention is to produce a silver halide emulsion that suppresses the generation of giant grains and miniaturizes the crystal grain size, and to produce a photographic light-sensitive material containing such a silver halide emulsion. The goal is to provide the following. Yet another object of the present invention is to provide a method for producing a silver halide photosensitive material comprising a silver halide emulsion with low fog. (Means for Solving the Problems) As a result of intensive studies, the object of the present invention is to provide a method for producing a silver halide photographic material comprising a silver halide emulsion, in which the silver halide emulsion is prepared by the following general formula (). A method for producing a silver halide photographic light-sensitive material, which comprises preparing a silver halide photographic material in the presence of a compound represented by the formula (), and then substantially converting the compound represented by the general formula () into the compound represented by the general formula (). It was found that this can be achieved by General formula () A(-L) _o --(-X) _n General formula () A(-L) _o --(-Y) _n In the formula, A represents a group that can be adsorbed to silver halide, L is a divalent organic group, X is a COOM group, SO ₂ M
group, [Formula] group, or a group convertible to OH group, Y is COOM group, SO ₃ M group,
[Formula] represents a group or OH group, M represents a hydrogen atom, an alkali metal atom, quaternary ammonium or quaternary phosphonium, n represents 0, 1 or 2, m represents 0, 1, 2, 3, Represents 4 or 5. Next, general formula () will be explained in detail. Specifically, the group represented by A in the general formula () includes mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptothiadiazoles, mercaptooxadiazoles, mercaptobenzimidazoles, and mercaptobenzthiazoles. , mercaptobenzoxazoles, benztriazoles, benzimidazoles, indazoles, tetraazaindenes, triazaindenes, guanines, adenines, and thioureas. The divalent organic group represented by L is specifically a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and in the middle, an ether bond, an ester bond, a thioether bond, an amide bond, a ureido bond, an imide bond, etc. The divalent group may be formed through a bond, a sulfone bond, a sulfonamide bond, a carbonyl bond, or the like, or a plurality of these bonding groups, alkylene groups, and arylene groups may be connected to form a divalent group as a whole. Further, when L contains a carbon atom, it is preferably 15 or less, more preferably 10 or less. The group represented by X in general formula () is preferably represented by general formula (D-1), (D-2), (D-3), (D-4),
(D-5) and (D-6). General formula (D-1) −COOR′ General formula (D-2) −SO ₃ R ₂ General formula (D-3) −SO ₂ R ₃ General formula (D-4) [C] General formula (D-5 ) -OR ⁵ General formula (D-6) In the formula, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are substituted or unsubstituted alkyl groups (preferably having 1 to 10 carbon atoms,
For example, methyl group, ethyl group, 2,3-dichloropropyl group, 2,2,3,3-tetrafluoropropyl group, butoxycarbonylmethyl group, methoxyethyl group, cyanoethyl group, methylsulfonylethyl group, methoxycarbonylethyl group, propargyl group, etc.), substituted or unsubstituted aryl groups (preferably having 6 to 10 carbon atoms, such as phenyl group, 3,4-methyleneoxyphenyl group, p-methoxyphenyl group, p-dianophenyl group, m-
nitrophenyl group, etc.), substituted or unsubstituted aralkyl groups (preferably having 7 to 12 carbon atoms, such as benzyl group, p-acetoxybenzyl group, p-nitrobenzyl group, etc.), substituted or unsubstituted alkenylene groups (preferably has 2 to 10 carbon atoms, such as a cyclopentenone group or a butenone group). R ³ is a substituted or unsubstituted alkyl group (preferably having 1 to 10 carbon atoms, such as methyl group, ethyl group, 2,3-dichloropropyl group, 2,2,3,
3-tetrafluoropropyl group, butoxycarbonylmethyl group, cyanoethyl group, methylsulfonyl group, methoxycarbonylethyl group, etc.), substituted or unsubstituted aryl group (preferably 6 to 6 carbon atoms)
10, such as phenyl group, 3,4-methyleneoxyphenyl group, p-methoxyphenyl group, p
-cyanophenyl group, p-nitrophenyl group, etc.), substituted/unsubstituted aralkyl group (preferably has 7 to 12 carbon atoms, such as benzyl group, p-acetoxybenzyl group, p-nitrobenzyl group, etc.); unsubstituted; alkenylene group (preferably having 2 to 10 carbon atoms, such as cyclopentenone group, butenone group, etc.), halogen atom (fluorine,
chlorine, bromine, etc.) and heterocyclic groups (eg, imidazolyl group, pyrazolyl group, pyro group, etc.). Also, when there are two or more X's, they may be the same or different. Among the compounds represented by the general formula (), the following can be preferably mentioned. General formula (P-1) [Formula] General formula (P-2) [Formula] General formula (P-3) [Formula] General formula (P-4) [Formula] General formula (P-5) [Formula] In the formula, G ₁ is a hydrogen atom, a halogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.), an acylamino group (e.g. benzamide group, hexane amide group), an alkoxy group (e.g. methoxy group, benzyloxy group), a sulfonamide group. (e.g. methanesulfonamide group, benzenesulfonamide group),
Aryl group (e.g. phenyl group, 4-chloroanil group), alkylthio group (e.g. methylthio group, butylthio group), alkylamino group (cyclohexylamino group etc.), anilino group (anilino group,
4-methoxycarbonylanilino group, etc.), amino group, alkoxycarbonyl group (methoxycarbonyl group, butoxycarbonyl group, etc.), acyloxy group (e.g. acetyl group, butanoyl group, benzoyl group, etc.), nitro group, cyano group, sulfonyl group (butanesulfonyl group, benzenesulfonyl group, etc.), aryloxy group (phenoxy group, naphthyloxy group, etc.), hydroxy group, thioamide group (butanethioamide group, benzenethiocarbonamide group, etc.), carbamoyl group (carbamoyl group, N-aryl group, etc.) carbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N-arylsulfamoyl group, etc.), carboxyl group, ureido group (ureido group, N-ethylureido group, etc.) or aryloxycarbonyl group (phenoxycarbonyl group, -methoxycarbonyl group, etc.). l represents an integer of 1 or 2. V ₁ represents a nitrogen atom or a methine group, and V ₂
represents an oxygen atom, an ionic atom, [formula] or [formula]. G ₂ is a substituent listed in G ₁ or (-L) _o --(-
X) represents _n . _G3 is a hydrogen atom, an alkyl group (e.g. methyl group,
ethyl group) or an aryl group (eg, phenyl group, naphthyl group). At least one of the groups represented by V ₂ and G ₂ is a group containing X. Also, when G ₁ , G 2 or G ₃ in (P-1), (P- ₂ ), (P-3), (P-4) and (P-5) contains an alkyl group moiety, alkyl The group may have 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms, and may be substituted or unsubstituted, linear or branched, linear or cyclic, saturated or unsaturated. Further, when G ₁ G ₂ or G ₃ contains an aryl group, the aryl group has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group. Specific examples represented by the general formula () used in the present invention are listed below. [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] ] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] Based on EJBirr's "Stabilization of Photographic Silver Halide Emulsions"
(Stabilization of Photographic Silver Halide
Focal Press
Company 1974, CG Barlow
et al., Research Disclosure No. 17643 (1978), U.S. Patent No. 2585388, U.S. Pat.
No. 21842, Japanese Patent Application Publication No. 53-50169, British Patent No.
No. 1275701, D.A. Burgess et al.
Berges et al), Journal of Heterocyclic Chemistry
Heterocyclic Chemistry) Volume 15, No. 981 (1978
The Chemistry of Heterocyclic Chemistry
Heterocyclic Chemistry, Imidazole and
Derivatives) part, pp. 336-9
Page, Chemical Abstracts
Abstract), 58 , No. 7921, p. 394 (1963), E. Hoggarth, Journal of Chemical Society.
Chemical Society), pp. 1160-7 (1949), S.R. Saudler,
W. Karo, Organic Functional Group Preparation
Preparation), Academic Press, pp. 312-5 (1968),
M.Chamdon, Bretan
Bulletin de la Societe Chemique de France
France), 723 (1954), DAShirley, D.A.
W. Alley), Journal of American Chemical Society
Chemical Society) 79 , 4922 (1954), A.
Wall Double March World (A.
Wohl.W.Marchwald), Bericht,
22, 568 (1889), P.C. Guha (PC
Guha), Journal of American Chemical Society
Chemical Society), 44 , 1502-10 (1922), U.S. Pat.
Advanced in Heterocyclic Chemistry, 9 ,
165-209 (1968), West German Patent No. 2716707, The
The Chemistry of Heterocyclic Compounds
Compounds), Imidazole and Derivatives, 1 .
384, Organic Synthesis (Org.Syntn.)
．． , 569 (1963), L.B. Cebrell (LB
Sebrell), CEBoord,
Journal of American Chemical Society
Society) 45 , 2390 (1923), JP-A-50-89034,
It can be synthesized by referring to the documents of 53-28426, 55-21007, and Japanese Patent Publication No. 40-28496, and the documents cited in these documents. Next, the substituent represented by X can generally be synthesized by the following method. This will be explained below using an example. For example, esters can be produced by reacting an acid halide with an alcohol compound or a phenol compound, by dehydrating a carboxylic acid with an alcohol compound or a phenol compound in the presence of DCC, or by reacting a carboxylic acid with an alcohol compound with an acid catalyst (such as sulfuric acid, hydrogen chloride, etc.). , BF ₃ , etc.) or the reaction of an acid anhydride with an alcohol compound or a phenol compound. The sulfonic acid ester can be obtained by combining a sulfonic acid halide and an alcohol compound or a phenol compound in the presence of a base (eg, pyridine, etc.). The phosphonic acid ester can be obtained from a phosphonic acid halide and an alcohol compound or a phenol compound in the presence of a base (for example, pyridine). Next, specific synthesis examples will be shown, but the invention is not limited thereto. Synthesis Example 1 Synthesis of Exemplary Compound (7) 2 g of 1-(4-carboxyphenyl)-5-mercaptotetrazole and 1.1 g of p-dianophenol
Dissolve g in 20 ml of pyridine or solution, add 0.05 g of p.
- Add toluenesulfonic acid, then at room temperature
2.3g dicyclohexylcarbodiimide in DMF
The solution was slowly added dropwise. After further stirring for 6 hours, dicyclohexylurea was removed by filtration, the filtrate was concentrated under reduced pressure, acetonitrile was added to the concentrate, and after cooling, the precipitated crystals were filtered. Further recrystallization from acetonitrile yielded 0.6 g of Exemplified Compound (7) as a pale yellow powder. Melting point: 178°C Synthesis Example 2 Synthesis of Exemplified Compound (4) Dissolve 1 g of 1-(3,5-dicarboxyphenyl)-5-mercaptotetrazole in 30 ml of methanol, add 0.1 ml of concentrated hydrochloric acid, and reflux for 8 hours. did. After cooling, methanol was removed under reduced pressure, and sodium chloride water was added to make the mixture alkaline, followed by extraction with ethyl acetate. The aqueous layer was made acidic again with hydrochloric acid, and after cooling, the precipitated crystals were filtered, and the white powder of Exemplified Compound (4) was obtained.
Obtained 0.7g. Melting point 151℃ Synthesis Example 3 Synthesis of Exemplary Compound (5) In a solution of 2 g of 1-(3,5-dicarboxyphenyl)-5-mercaptotetrazole and 1.2 ml of ethylene cyanohydrin dissolved in 10 ml of pyridine,
0.05 g of p-toluenesulfonic acid was added, and then 3.7 g of a PMF solution of dicyclohexylcarbodiimide was slowly added dropwise at room temperature. After stirring for an additional 4 hours, dicyclohexylurea was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was separated by column chromatography, and the exemplified compound was obtained as a pale yellow powder.
1.1g of (5) was obtained. Melting point: 128°C Synthesis Example 4 Synthesis of Exemplified Compound (16) 10 g of 5-carboxy-1,2,3-benzotriazole and 8 g of p-chlorophenol were added to 20 ml of
0.2 g of dimethylaminopyridine was added to the solution dissolved in PMF, and a PMF solution of 14 g of dicyclohexylcarbodiimide was slowly added dropwise at room temperature. Thereafter, the mixture was heated to 50 to 60°C, stirred for 4 hours, allowed to cool, dicyclohexylurea was removed by filtration, and the filtrate was poured into water. The precipitated crystals were filtered and recrystallized with CHCl ₃ to give the exemplified compound (1
4.5g of 6) was obtained. Melting point: 160°C Synthesis Example 5 Synthesis of Exemplary Compound (18) 7-Hydroxy-5-carboxymethyl-[1,
To a solution of 15 g of 2,4]-triazolo-[1,5,a]-pyrimidine and 12.3 g of phenol dissolved in 80 ml of pyridine, 0.2 g of p-toluenesulfonic acid was added, and then 21 g of dicyclohexyl was added at room temperature. A PMF solution of carbodiimide was slowly added dropwise. After stirring for an additional 6 hours, dicyclohexylurea was removed by filtration, and the filtrate was concentrated under reduced pressure. CHCl ₃ was added to the concentrate, and after cooling, the precipitated crystals were filtered. Further, it was recrystallized from CHCl ₃ to obtain 10 g of Exemplified Compound (18) as a pale yellow powder. Melting point: 186°C Synthesis Example 6 Synthesis of Exemplary Compound (21) 7-Hydroxy-5-carboxymethyl-[1,
To a solution of 15 g of 2,4]-triazolo-[1,5,a]-pyrimidine and 13 ml of n-hexyl alcohol dissolved in 80 ml of pyridine, 0.2 g of p-toluenesulfonic acid was added, and then 21 g of dicyclohexyl was added at room temperature. A PMF solution of carbodiimide was slowly added dropwise. After stirring for an additional 3 hours, dicyclohexylurea was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was recrystallized from a small amount of CHCl/n-hexane to obtain 15 g of exemplified compound (21) as a white powder. Melting point: 119° C. As a method for converting the compound of general formula (), which is the essence of the present invention, into a compound of general formula (), it is common to use a pH change or use various nucleophilic substances. Examples of alkalis used for pH change include inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, calcium hydroxide, barium hydroxide, etc.), nitrogen-containing compounds (ammonia, methylamine, aniline,
Examples of acids include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, p-
Examples include toluenesulfonic acid. Examples of nucleophilic substances include sulfite ion, hydroxylamine, thiosulfate ion, metabisulfate ion, hydroxamic acid and its analogues, and oxy compounds. When converting a compound of general formula () to a compound of general formula () using a pH change, it does not matter what pH is used as long as the conversion occurs, but it is usually carried out between 2.0 and 10.0. is desirable. Especially high
When PH treatment is required, PH8 or higher, preferably PH
8.0 to 10.0, preferably PH 2.0 to 4.0 when low PH treatment is required, and more preferably PH 2 to 3.5. When using a nucleophilic substance, the amount of the nucleophilic substance used can be added depending on the amount of the compound of general formula () used. When complete conversion is required, it is necessary to add at least an equivalent amount to the compound of general formula (), and when it is desired to deactivate only the required amount, the amount added may be adjusted accordingly.
For example, 1/10 to 5×10 ² times equivalent can be used. The temperature and time of the reaction for converting the compound of general formula () into the compound of general formula () can be selected so that the conversion reaction occurs as many times as necessary. Although it depends on the pH of the reaction, the type and amount of the nucleophilic substance, and the type of compound represented by the general formula (), it is generally desirable to set the temperature at 30°C to 90°C and the time between about 1 minute and 100 hours. The amount of the compound of general formula () to be added in the present invention can be freely determined depending on the type of compound used and the timing of addition, but it ranges from 10 ^-7 mol to ^{10 -1} mol per mol of silver halide.
mol is preferred, and ^10-6 mol to ^10-2 mol is more preferred. The compound of general formula () may be converted to the compound of general formula () at any time after the addition of the compound of general formula () and immediately before application. Further, depending on the case, the conversion may be carried out by the above-mentioned treatment after coating and before using the light-sensitive silver halide photographic material of the present invention. Next, preferred embodiments of the method for converting the compound of general formula () into the compound of general formula () will be described. Silver halide emulsion grain formation is carried out in the presence of the compound of general formula () to form a fine-grain emulsion without macrograins, and until immediately before coating (preferably,
(before the start of chemical ripening), it is converted into a compound of general formula (). Forming silver halide emulsion grains in the presence of a compound of general formula () to form a silver halide emulsion with good monodispersity,
It is converted into a compound of general formula () immediately before application (preferably before the start of chemical ripening). When silver halide emulsion grains are formed in the presence of the compound of the general formula (), a silver halide emulsion with a unique crystal habit that is normally difficult to obtain is formed, and the silver halide emulsion is formed until immediately before coating (preferably from the start of chemical ripening). ) is converted into a compound of general formula (). Silver halide emulsion grains are formed in the presence of a compound of the general formula () to form silver halide emulsion grains with few fog nuclei, and immediately before coating (preferably before the start of chemical ripening), a compound of the general formula ( ) is converted into the compound. Chemical ripening is performed in the presence of the compound of general formula () to convert it to the compound of general formula () immediately before coating. In the present invention, since the compound of the general formula () has much weaker adsorption to silver halide grains than the compound of the general formula (), its effect is reduced when converted to the compound of the general formula (). We believe that this has made it much weaker and has made it possible to eliminate the adverse effects of using compounds that adsorb to silver halide, but elucidating the detailed mechanism is a future challenge. This action can reduce or eliminate the effects of chemical ripening. Furthermore, inhibition of adsorption of various additives such as sensitizing dyes can be prevented, and since the compound of general formula () is not carried in until the time of development, the development inhibition effect can be eliminated. In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any silver halide including iron bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. The grain size of the silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. Silver halide photographic emulsions that can be used in the present invention are:
It can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), 22
~Page 23, “Emulsion preparation
and types)” and same, No. 18716 (November 1979),
The method described on page 648, "Physics and Chemistry of Photography" by P. Glafkides, published by Paul Montell.
Chimie et Physique Photographique Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (GFDuffin,
Photographic Emulsion Chemistry (Focal
Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VLZelikman
et al, Making and Coating Photographic
Emulsion, Focal Press, 1964). That is, any method may be used, such as acidic method, neutral method, ammonia method, etc., and methods for reacting soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used.
It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and PH during grain formation. For more information, see Photographic Science and Engineering Vol.
Volume, pp. 159-165 (1962); Journal of Photographic Science
Photographic Science), Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3655394 and British Patent No.
Described in No. 1413748. Furthermore, as a monodisperse emulsion, the average particle diameter is approximately
Emulsions with silver halide grains larger than 0.1 micron, at least 95% by weight of which are within ±40% of the average grain diameter are typical. Average particle diameter is 0.25-2 microns and at least 95% by weight
Alternatively, an emulsion in which at least 95% of the silver halide grains in number are within the range of ±20% of the average grain diameter can be used in the present invention. Methods for making such emulsions are described in US Pat. No. 3,574,628, US Pat. No. 3,655,394 and British Patent No. 1,413,748. Also, JP-A No. 48-8600, No. 51-39027, No. 51-83097,
No. 53-137133, No. 54-48521, No. 54-99419
Monodisperse emulsions such as those described in Japanese Patent No. 58-37635 and Japanese Patent No. 58-49938 can also be preferably used in the present invention. Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Average particles are defined by Gutoff, Photographic Science and Engineering.
Science and Engineering), Volume 14, 248-257.
Page (1970); U.S. Patent Nos. 4434226 and 4414310
No. 4433048, No. 4439520 and British Patent No.
It can be easily prepared by the method described in No. 2112157. The use of tabular grains has advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as detailed in U.S. Pat. No. 4,434,226 cited above. ing. The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1027146, US Patent No. 3505068;
4444877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. These emulsion grains are described in U.S. Pat.
No. 4459353, UK Patent No. 2038792, US Patent No. 4349622, US Patent No. 4395478, US Patent No. 4433501, US Patent No.
No. 4463087, No. 3656962, No. 3852067, JP-A-Sho
No. 59-162540, etc. Also, mixtures of particles of various crystal forms may be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see, for example, "Dei Grantragen" edited by H. Frieser.
Dell Photography Processor
Mituto Zilbel Halogenyden (Die)
Grundlagen der Photographischen Prozesse
mit Silber-halogeniden)
Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur-containing compounds that can react with activated gelatin and silver (e.g. thiosulfates, thioureas,
sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), cyclic sensitization method using noble metal compounds (e.g. In addition to gold compounds, a noble metal sensitization method using complex salts of group metals of the periodic table, such as platinum, iridium, and palladium, can be carried out alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles {for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroimidazoles,
benzotriazoles, aminotriazoles, etc.}; mercapto compounds {for example, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
mercaptopyrimidines, mercaptotriazines, etc.}; thioketo compounds such as oxadolinthione; azaindenes {e.g., triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraaza A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.), pentaazaindenes, etc.); The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, 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 nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. Merocyanine dyes or composite merocyanine dyes include a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbin nucleus. A 5- to 6-membered heteroartic ring nucleus such as a tool acid nucleus can be applied. The aforementioned additives are found in Research Disclosure Vol. 176 No. 17643 (December 1978) and Vol. 187 of the same.
No. 18716 (November 1979), and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below. [Table] When the silver halide photosensitive material of the present invention is a color photosensitive material, various color couplers can be used. , -C~G
It is described in the patent described in . As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, agenta, and cyan) in subtractive color development are important. Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers include the aforementioned RD17643,
In addition to the couplers described in the patents listed in Sections -C and D, the following can be preferably used in the present invention: A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4022620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4401752, U.S. Pat.
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density. Magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl couplers, preferably 5-pyrazolone and pyrazoloazole couplers, which have a ballast group. A 5-pyrazolone coupler in which the 31st position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.
It is described in No. 2311082, No. 2343703, No. 2600788, No. 2908573, No. 3062653, No. 3152896, No. 3936015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler,
Preferred are nitrogen atom leaving groups as described in US Pat. No. 4,310,619 or arylthio groups as described in US Pat. No. 4,351,897. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73636 provides high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,879, preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. No. 3,725,067; Research Disclosure 24220 (June 1984)
and pyrazolotetrazoles and research disclosure described in JP-A No. 60-33552.
24230 (June 1984) and pyrazolopyrazoles described in JP-A-60-43659. Imidazo[1,
2-b] Pyrazoles are preferred, as described in European Patent No.
Pyrazolo [1,5-b] [1,
2,4] triazoles are particularly preferred. Cyan couplers that can be used in the present invention include:
Hydrophobic, diffusion-resistant naphthol and phenolic couplers include the naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. A typical example is the oxygen atom dissociating type two-equivalent naphthol coupler described in the above issue. Specific examples of phenolic couplers include U.S. Patent No. 2369929, U.S. Patent No. 2801171,
It is described in No. 2772162, No. 2895826, etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is a phenolic coupler having an alkyl group equal to or higher than ethyl group at the meta position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan coupler, US Patent No. 2772162, US Patent No. 3758308, US Patent No. 4126396,
No. 4334011, No. 4327173, West German Patent Publication No.
3329729 and European Patent No. 121365, etc., and U.S. Pat. No. 3446622 and European Patent No.
These include phenolic couplers having a phenylureido group at the 21-position and an acylamino group at the 51-position, which are described in Nos. 4333999, 4451559, and 4427767. In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with a color photosensitive material for photographing. US Patent No.
Yellow-colored magenta couplers described in Japanese Patent Publication No. 4163670 and Japanese Patent Publication No. 57-39413, or U.S. Pat.
4004929, 4138258 and British Patent No.
Typical examples include the magenta-colored cyan coupler described in No. 1146368 and the like. Other colored couplers are described in Sections RD17643-G above. Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of magenta couplers are shown in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570.
Also, European Patent No. 96570 and West German Application No.
Specific examples of yellow, magenta or uncoupler are described in No. 3234533. The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in US Pat. No. 3,451,820 and US Pat. No. 4,080,211. Specific examples of polymerized magenta couplers are given in UK Patent No. 2102173 and US Patent No.
Described in No. 4367282. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned
The patent couplers described in RD17643, Sections ~F are useful. Suitable supports that can be used in the present invention include, for example:
Page 28 of the aforementioned RD.No.17643 and the same, No.18716
It is described from the right column on page 647 to the left column on page 648. The silver halide photosensitive material of the present invention includes a black and white silver halide photographic material (for example, an X-ray photosensitive material, a lithium-type photosensitive material, a negative film for black and white photography, etc.)
and color photographic materials (for example, color negative film, color reversal film, color paper, etc.). Further examples include light-sensitive materials for diffusion transfer (for example, color diffusion transfer elements, silver salt diffusion transfer elements), heat-developable light-sensitive materials (black and white, color), and the like. The photographic material according to the present invention includes the above-mentioned RD,
Development processing can be carried out by the usual method described in pages 28 to 29 of No. 17643 and the left column to right column of 651 of No. 18716. Further, the photographic material of the present invention can be generally subjected to water washing treatment or stabilization treatment after color development, bleach-fixing or fixing treatment. (Examples) The present invention will be specifically described below based on Examples. Example 1 While vigorously stirring Solution I kept at 45°C, 800 ml of silver nitrate aqueous solution (AgNO ₃ 120 g) and a mixed aqueous solution of sodium chloride and potassium bromide (NaCl 40.4 g,
A silver chlorobromide emulsion (silver bromide 2 mol %) was prepared by simultaneously adding 800 ml of KBr (1.7 g) over 10 minutes. Solution I Inactive Gelatin Sodium Chloride Rhodium Chloride Aqueous 20g 250mg 7.4mg 1 Here, a silver chlorobromide emulsion is prepared by adding the compound of the general formula () of the present invention to Solution I as necessary as shown in Table 1. After that, each of the emulsions was divided into two or three equal parts, one part was left as is, and the other part was treated as shown in Table 1. A portion of the emulsion was taken and the grain size and presence or absence of coarse grains were examined using an electron microscope. Examined. Results first
Shown in the table. After washing these emulsions with water in a conventional manner, stabilizers; 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene, a hardening agent; 2,4-dichloro-6-hydroxy-S-triazine sodium, and a coating aid; sodium dodecylbenzenesulfonate were added to coat a polyethylene terephthalate film support, and the coating amount was It was coated and dried at a concentration of 2.5 g/m ² . These samples 1 to 5 were fully exposed to light using a mercury lamp through a light wedge, and then developed with Kodatsu formulation D-72 developer at 27°C for 2 minutes and 10 seconds, followed by normal stopping and cooling.
It was fixed, washed with water, dried, and the maximum density (Dmax) was determined. The results obtained are shown in Table 1. As can be seen from the results in Table 1, this example is an example of producing a silver halide photosensitive material for use in a bright room. In order to increase the maximum density, it is necessary to make the silver halide particles finer. However, as is clear from Table 1, it is difficult to reduce the grain size of silver chloride using conventional methods (such as the rapid addition method), and coarse grains are also likely to be generated. Addition of the compound of the general formula () has the advantage of reducing the particle size and significantly reducing the number of coarse particles. However, since these compounds of general formula () cannot be removed by washing with water or the like, there is a problem that the maximum concentration is lowered by the development-inhibiting action of the compound of general formula (). However, as in the present invention, by converting the compound represented by the general formula () into the compound represented by the general formula (), an extremely large effect was obtained in that the maximum concentration was significantly increased. [Table] Example 2 Potassium thiocyanate was added to an aqueous gelatin solution kept at 50°C with vigorous stirring, and then an aqueous silver nitrate solution and a mixed aqueous solution of potassium bromide and potassium iodide were simultaneously added over 30 minutes. A silver iodobromide emulsion (iodity 1 mol %) was obtained. At this time, the compound of the general formula () of the present invention shown in Table 2 was added 5 minutes after the start of addition of silver nitrate, and immediately after the addition of silver nitrate was completed, it was added with sodium hydroxide under the conditions shown in Table 2. It was reacted and converted into a compound of general formula (). Note that the addition of the compound of general formula () of the present invention reduces the particle size, so the amount of potassium thiocyanate added is adjusted to reduce the particle size to 0.48μ.
tailored to. Next, after washing with water, adjust the pH to 6.4 and pAg to 8.8.
It was compound aged with sodium thiosulfate, rhodanpotash and potassium chloroaurate. The same stabilizers, hardeners and coating aids as in Example 1 were added to each of the resulting emulsions, which were then coated onto a cellulose triacetate film support and dried to obtain Samples 21-25. After exposure under a light wedge, it was developed with Kodak formulation D-19 developer at 20 DEG C. for 4 minutes, followed by the usual stopping, fixing, water washing and drying to give the results shown in Table 2. In Table 2, the relative sensitivity relatively represents the reciprocal of the exposure amount required to provide a density of "fog value + 0.5", and the sensitivity of sample 20 was assumed to be 100. In addition, undercutting is expressed as the difference in the logarithmic value of the exposure amount required to give a density of "fog value +0.1" and "fog value +0.5", and the smaller this value is, the more
Indicates that the foot is well cut (the gradation of the foot is hard). From the results shown in Table 2, the addition of the compound of general formula () eliminates the generation of coarse particles that were observed when no addition was made, and the particle size becomes more uniform. However, if left as is, the chemical ripening will be delayed and development will be inhibited due to the residual compound of the general formula (), and contrary to expectations, the undercut will worsen and the sensitivity will drop significantly. However, by converting the compound of the general formula () to the compound of the general formula () as in the present invention, the action of the compound of the general formula () used during particle formation can be deactivated, so it is also effective against chemical ripening. Since the inhibitory effect on development was eliminated, the torn-out effect was improved, and the sensitivity was also restored to the same level. [Table] Example 3 Sensitizing dye: 5,5'-dichloro-9-ethyl- 3,
3'-di(3-sulfopropyl)oxacarbocyanine sodium, magenta coupler; 1-(2,
4,6-trichlorophenyl)-3-[3-(2,
4-di-t-amylphenoxyacetamido)benzamide]-5-pyrazolone, stabilizer; 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, hardener; 1,3 -Bis-vinylsulfonylhydroxypropane, coating aid; sodium p-dodecylbenzenesulfonate, sodium p-nonylphenoxypoly(ethyleneoxy)propanesulfonate were added sequentially, and coated on a cellulose acetate film support. , dried sample
Got 30-3. Next, the film was exposed to light through a yellow filter under a light wedge, and the following color development process was performed to obtain the results shown in Table 3. The development used here was carried out at 38°C as described below. 1 Color development...1 minute 30 seconds 2 Bleaching...6 minutes 30 seconds 3 Washing...3 minutes 15 seconds 4 Fixing...6 minutes 30 seconds 5 Washing... …3 minutes 15 seconds 6 Stable …3 minutes 15 seconds The composition of the processing liquid used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Ammonia water (28%) 25.0cc Ethylenediamine-tetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0cc Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0cc Add water 1 As is clear from Table 3, in samples 32 and 34 in which the compound of general formula () was converted to the compound of general formula (), the adsorption of the sensitizing dye was as compared to samples 31 and 33 in which the compound of general formula () was converted into the compound of general formula (). ) is no longer inhibited by the presence of the compound, resulting in good spectral sensitization. 【table】

Claims (1)

[Scope of Claims] 1. In a method for producing a silver halide photographic material comprising a silver halide emulsion, the silver halide emulsion is prepared in the presence of a compound represented by the following general formula (), and then a general 1. A method for producing a silver halide photographic material, which comprises substantially converting a compound represented by the formula () into a compound represented by the general formula (). General formula () A(-L) _o --(-X) _n General formula () A(-L) _o --(-Y) _n In the formula, A represents a group that can be adsorbed to silver halide, L is a divalent organic group, X is a COOM group, SO ₃ M
represents a group that can be converted into a group, [Formula] group, or OH group, Y represents a COOM group, SO ₃ M group, [Formula] group, or OH group, and M represents a hydrogen atom, an alkali metal atom, or a quaternary ammonium atom. or represents a quaternary phosphonium, n represents 0, 1 or 2, and m represents 0, 1, 2, 3, 4 or 5.