JPS62186252A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material material having sufficiently large max. optical density and sufficiently small min. optical density, and a good shelf life stability and a high sensitivity by comprising at least one part of an internal latent image type silver halide particles which are formed by growing up a silver halide precipitate obtd. by mixing ammine silver complex salt and a soluble halide in the presence of a specific compd in the titled material. CONSTITUTION:At least one part of the internal latent image type silver halide particles is formed by growing up the new silver halide precipitate obtd. by mixing ammine silver complex salt and a soluble halide. The internal latent image type silver halide particle is formed in the presence of at least one of compds selected from the compd. shown by formula (I), (II), (III) or (IV) and the compd. having a repeating unit shown by formula (V). In the formulas, R1, R2 and R3 may be identical or different with each other, and are each hydrogen atom, halogen atom or hydroxy group, etc., X is a monovalent group except hydrogen atom from the compd. shown by formula (I), (II), (III) or (IV). J is a bivalent linkage group.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a direct positive silver halide photographic light-sensitive material, and more specifically, after image exposure, the present invention relates to a direct positive silver halide photographic light-sensitive material. The present invention relates to a photographic material having an internal latent image type silver halide emulsion layer from which a direct positive image can be obtained.

[Conventional technology]

Conventionally known methods for obtaining direct positive images are mainly divided into two types. One type uses a silver halide emulsion that has fogged nuclei in advance, and utilizes solarization or the Burschel effect.
By destroying the fogging nuclei or latent image in the exposed area, a blurred image is obtained after development. Another type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and performs further processing (development nucleation treatment) after image exposure, and then surface development, or fogging after image exposure. A positive image can be obtained by performing surface development while undergoing processing (development nucleation processing). The above-mentioned process (J') (development nucleation process) may be performed by exposing the entire surface to light, chemically using a fogging agent, or using a strong developer.
Furthermore, heat treatment or the like may be used. Of the above two methods for forming a positive image, the latter type of method generally has higher sensitivity than the former type of method, and is suitable for applications requiring high sensitivity. Various techniques are known in this technical field. For example, regarding this type of /% silver lodenide emulsion, see US Pat.
-34213, 58-1412 and 58-14
Conversion type, core shell type, or 11 type is disclosed in No. 15, etc., and thioether, imidazole, etc. are used as particle growth agents in U.S. Pat. No. 3,574,629 or JP-A-5
4-100717, etc.

[Problems to be solved by the invention]

Although it is possible to produce photographic materials that form positive images by using these known techniques, further improvement in photographic performance is desired in order to apply these photographic materials to various photographic fields. There is. For example, U.S. Pat. Nos. 3,761,267 and 3,20
Higher sensitivity can be obtained by chemically sensitizing the interior of silver halide grains or by using a core/shell type emulsion doped with polyvalent metal ions, as disclosed in No. 6,318. However, this type of emulsion has the disadvantage of low image density. . Further, U.S. Pat. No. 3,761,276 discloses that the surface of silver halide grains is subjected to a certain degree of chemical ripening treatment in order to improve the above-mentioned drawback of low image density. This is disadvantageous because the silver halide emulsion has a high value of 100% and has very poor long-term storage stability, and also has poor production stability. On the other hand, with the silver halide emulsion mainly composed of silver chloride disclosed in JP-A No. 47-32820, the maximum density of the obtained positive image is relatively high, but the minimum density is not sufficiently small and the image is unclear. The result is a strange image. In addition, these emulsions require a long time to prepare without the use of the grain growth agents, while on the other hand, if grain growth agents such as thioether, substituted thiourea, or imidazole are used, the minimum concentration is high and storage stability is poor. It has the following disadvantages. Accordingly, an object of the present invention is to provide a high-sensitivity internal latent image type silver halide photographic light-sensitive material that has a high maximum density, a low minimum density, good storage stability, and high sensitivity.

[Means for Solving the Problems] In accordance with the above-mentioned object of the present invention, as a result of studying mainly the structural conditions of silver halide grains, an internal latent image type/) lodenization in which the grain surface is not fogged in advance has been found. It has at least one silver lodenide emulsion layer containing silver particles, and a positive image can be obtained directly by surface development after image exposure, or after and/or while carrying out fogging treatment. In the photographic light-sensitive material, at least a part of the internal latent image type/transparent silver grain structure undergoes a growth process by a novel silver decadenide precipitation by mixing an ammine silver complex salt and a soluble halide, and the above-mentioned The internal latent image type silver halide grains have the following general formulas (I), (IF) (■
), or NV) and the following general formula (V)
A silver halide photographic light-sensitive material of general formula (1) characterized in that it is carried out in the presence of at least one compound selected from compounds having a repeating unit represented by
General formula (II) General formula (1) General formula (IV) General formula (V3 R6 (CH2-C) In the formula, R+ = R2 and R5 may be the same or different, and each represents a hydrogen atom, a halogen atom, or a hydroxyl atom. group, ami7 group, derivative of ami7 group, alkyl group, derivative of alkyl group, aryl group, derivative of aryl group, cycloalkyl group, derivative of cycloalkyl group, mercapto group, derivative of mercapto group, or - CONH-R, (R is a hydrogen atom, a furkyl group, an amine 7 group, a furkyl group derivative, an amine 7 derivative, a halogen atom, a cycloalkyl group, a cycloalkyl group derivative, an aryl group or an aryl group derivative) ), R3 and R1 may be combined to form a ring, R5 represents a hydrogen atom or an alkyl group, and X represents the general formula (I), (If), (I[[
) or (IV) from which one hydrogen atom has been removed, the monovalent group J represents a divalent linking group. In the embodiment of the present invention, the precipitation by the ammine complex salt and the soluble halide is performed at pH≦10, preferably at p1.
19, while neutralizing to a range of 5 to 6.0, and pAg
It is preferable to maintain the range between 6 and 9. The silver halide composition may be any silver halide composition. Examples include silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloride, and hot spring silver iodide. In the silver halide composition, silver chloride is preferably 0 to 100 mol%, preferably 0 to 75 mol%, more preferably 0 to 50 mol%, and silver iodide is preferably 0 to 10 mol%. . The structure of the emulsion grains is preferably core-shell type or laminated grains consisting of an inner core and at least one outer shell, and it is further preferred that the inner core contains at least 650 mol % of silver bromide. Further, the emulsion particle size is 0.1 to 2.0 μl, preferably 0.1 to 2.0 μl.
2~1.5μ! and preferably has a monodisperse particle size distribution. In the case of core-shell type particles, the inner core is preferably doped with polyvalent metal ions and chemically sensitized, and the ratio of the outer shell to the entire particle is preferably 20 to 99 mol%. -For layered grains in which a delivery singularity is formed at the layered interface, it is preferable to have different silver halide compositions in the inner core and outer shell to provide a difference of 30 mol% or more in silver chloride content. . The ammine silver complex used in the present invention is obtained by adding ammonia in an amount equivalent to or more than the amount required to form the complex to an aqueous silver nitrate solution to form a silver-ammonia complex.The feature of the present invention is that a silver ion-containing solution and a halide solution are mixed. When producing silver halide containing silver chloride, an ammoniacal silver nitrate solution containing the ammine silver Iff salt is used to produce at least a portion of the silver halide, and the ammoniacal silver nitrate solution is represented by the general formulas (1) to (V). The purpose is to cause the compound to coexist when forming silver halide grains. Furthermore, the monodispersity referred to in the present invention refers to the surface area r'' that determines the amount of light received, the amount of ripening or processing effects that have a profound effect on the photographic properties of emulsion grains, and the photographic Focusing on the fact that the volume r3, which is involved in the density of the origin of the effect, and the number n of grains having the grain size r, dominantly determines the characteristics of the photographic emulsion containing the grains, Since r is useful for intuitive understanding, as a representative value that effectively represents the characteristics of the emulsion grains, the horizontal axis represents the individual grain section molecule i, and the vertical axis represents the volume r31, which represents the frequency ni of the section.
The weighting given as a weight is based on the frequency n1r3i. The mode rm was taken as the standard for monodispersity. In the present invention, 60% of the total silver halide grain weight is set within the grain size r4 range with a grain size deviation of ±20% around the mode rm defined above. It is considered monodisperse when it contains particles of 70% or more.In the present invention, monodispersity is defined as 70% or more, preferably 8.
It is 0% or more. Next, the present invention will be explained in detail. In the general formulas (1) to (V), examples of the alkyl group represented by R8-R4 include methyl group, ethyl group, propyl group, pentyl group, hexyl group, octyl group,
Isopropyl group% 5ea-butyl group, L-butyl group,
Examples of alkyl group derivatives include alkyl groups substituted with aromatic residues (possibly via a divalent linking group such as -NIICO-) (e.g. benzyl group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkyl groups substituted with alkoxy groups (e.g. methoxybutyl group, 2-methoxybutyl group, 3-ethoxypropyl group) , 4-methoxybutyl group, etc.), halogen atom, hydroxy group, carboxy group,
A mercapto group, an alkoxycarbonyl group, or an alkyl group substituted with a substituted or unsubstituted amino group (e.g., monochloromethyl group, hydroxymethyl group, 3-hydroxybutyl group, carboxylder group, 2-carboxyethyl group, 2- (methoxycarbonyl)ethyl group, aminomethyl group, diethylamide group, etc.), an alkyl group substituted with a cyfcol alkyl group (e.g. cyclopendelmethyl group, etc.), a group represented by the above general formulas (1) to (■). Examples include an alkyl group substituted with a monovalent group obtained by removing the hydrogen atom IFi from the compound. Examples of the aryl group represented by R7-R4 include phenyl group and l-naphthyl group, and examples of derivatives of the aryl group include p-)lyl group, yama-nibruphenyl u, m-cumenyl group, and mesidel group. group, 2.3-xylyl group, p-chlorophenyl group, 0-bromophenyl group,
p-hydroxyphenyl group,! -Hydroxy-2-naphthyl group, m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, 0-(methoxycarbonyl)phenyl group, m-(ethoxycarbonyl)phenyl group, 4-carboxy-1-naphthyl group Examples include groups. Examples of the cycloalkyl group represented by 11 I-n 4 include a cyclohebutyl group, a cyclopentyl group, a cyclohexyl group, and ffl of the cycloalkyl group.
Examples of the G-isomer include methylcyclohexyl group. Examples of the halogen atom represented by Rl-R4 include fluorine, chlorine, bromine, and iodine, and examples of derivatives of the amino group represented by R8-R4 include butylamino, diethylamino, and anilino groups. n
Examples of the mercapto group derivative represented by , -1Z3 include methylthio group, ethylthio group, phenylthio group, and the like. The alkyl group represented by Rs preferably has a carbon number of i to
6, and examples thereof include methyl group and ethyl group. Especially preferred as R is a hydrogen atom and a methyl group. Although J is a divalent linking group, it is preferable that the total number of carbon atoms is 1 to 20. Among such linking groups, the following formula (J
-I) or (J, -41) is preferred. (J-1) (J-H) In the formula, Y represents 10- or -N- (here, rts is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). Z is an alkylene group (preferably one with up to 10 carbon atoms. An amide bond, ester bond, or ether bond may be interposed between the alkylene groups. For example, a methylene group, ethylene group, propylene group, CLOCllt
, C11*C0N)IC11*, C1
1tCILCOOCII-, C0ICIItOCOCI
I*, C11tNHCOCIIt-, etc.) -〇-
Alkylene group, -〇〇NI+-alkylene group, -COO
-alkylene group, -0CO-alkylene group or -N
I[CO-alkylene group (these alkylene groups preferably have up to 10 carbon atoms) or (yo-alkylene group (
Preferably it has 6 to 12 carbon atoms. For example, p-phenylene group, etc.). Particularly preferable divalent linking groups as J include the following. C0NIICII*, -C0NIICI*CII
*, C0NICIItOCOCL. C0NIICI[, CIItCIItOCOCIlt
, °C00CHt, C00CHzC1b
. -C00C11, CIl, 0COCI+! +, -CO
OCIIICIIffiCl [tOCOCH, -. The compound represented by the general formula (V) may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, meccrylamide, acrylic ester, and methacryl ester. Next, a compound represented by the general formula (1), (II), (III') or (TV) or the general formula (
A compound having a repeating unit represented by V) (hereinafter referred to as
(referred to as the tetrazaindene compound used in the present invention)
A typical example is shown below. O■ 0■ (Engineering 6) n++ 1ll y: 5 to 50 mol% copolymer 1ll y: 5 to 50 mol% copolymer υH y: 5 to 50 mol% copolymer υIt y : 5 to 50 mol% of the copolymer The above-mentioned compound according to the present invention (hereinafter simply referred to as a tetrazaindene compound) is pre-existing in the mother liquor during the formation of a silver decadenide emulsion, and It is preferable to increase the amount added as particles are generated and grown. Therefore, the tetrazaindene compound of the present invention is preferably added to the mother liquor of emulsion mixing and /10 denide ion solution (hereinafter referred to as /1 ride solution) (1 is preferably added to the ammoniacal silver nitrate solution, and separately, the present invention It is also preferable to prepare a solution of the tetrazaindene compound and inject it into the emulsion together with a halide solution and/or an ammoniacal silver nitrate solution. is the most preferable in terms of simplifying the process and increasing productivity. By changing the amount of mixed mother liquor and tetrazaindene supplied during silver halide grain JA fjc, the history of crystal habit during silver halide crystal growth and The shape (crystal habit) of the final particles can be controlled. The amount of the tetrazaindene compound added varies depending on the grain size of the silver halide grains to be obtained, the composition of the silver halide, the temperature during emulsion creation, pH, pAg, etc., but 101-2X per mole of silveride
A range of 10-' moles is preferred. In the method of the present invention, a halide solution and an ammoniacal silver nitrate solution are mixed in the presence of a tetrazaindene compound as described above to form a silver halide emulsion. A silver-ammine complex solution is obtained by adding more than an equivalent amount of ammonia, and when ammoniacal silver nitrate is used, at the moment the solution is added to the mixture, the silver-ammine complex is overwhelmingly large, and free silver is present. The i-ion concentration is much smaller than when silver nitrate solution is added directly, and the production of silver oxide is extremely small, so it is less likely to be reduced to metallic silver (coupled with the effect of the tetrazaindene compound, a strong capri On the other hand, when an ammonia-silver heptanitrate solution is used, a large amount of ammonia is brought into the mixture of the silver ion solution and the halide solution, resulting in a high PL+ of the solution, but an emulsion containing silver chloride If the format is carried out at too high a pH, fogging may increase, and the pH of the mixture when mixing the ammoniacal silver nitrate solution and the rodenide ion solution is preferably 10 or less, more preferably 6.
It is recommended that the temperature be maintained at ~9.5. 1) In order to maintain 11 in the above state, add an appropriate amount of acid in advance to the protective colloid solution and/or denide ion solution, which is the mother liquor of the mixed solution of ammoniacal silver nitrate solution and halide ion solution. Alternatively, an acid solution may be added continuously or intermittently to the mixed solution as the mixing progresses. As the acid used to adjust the pH, various acidic substances can be used, such as inorganic acids such as sulfuric acid and nitric acid, acetic acid, and citric acid. In the method of the present invention, the crystal habit, shape, etc. of the silver halide grains obtained change depending on the amount of the tetrazaindene compound depending on the amount of the tetrazaindene compound during the formation of the silver halide grains. The crystal habit, particle size distribution, and shape of crystals are described in the Journal of Photographic Science.
5science) Vol. 12, pp. 245-251 (1964
), Vol. 27, pp. 47-53 (1979), and many other publications, it depends on the silver ion concentration in the solution at the time of crystal formation, that is, pAg. In the emulsion according to the present invention, it is preferable to maintain p/Ig of the mixed solution within the range of 4 to 9 throughout the grain formation process, including the time of mixing the ammoniacal silver nitrate solution and the halide ion solution. 91 g may be kept at a constant value within the above range throughout the mixing period depending on the crystal habit, shape, particle size distribution, etc. of the grains of the silver halide emulsion to be obtained; It may be changed during the process of adding the silver ion solution as described. l) As a method for controlling Ag, it is preferable to use a mixed solution of water-soluble bromide ions and water-soluble chloride ions as the pAg control liquid. That is, the amount of halide ions added per unit time during mixing is approximately equal to the amount of silver ions added, and at the same time, the pAg control liquid consisting of the mixed solution of water-soluble bromide ions and chloride ions is adjusted to the ratio shown by the following formula. Add at pA
It is preferable to control the FI value from the viewpoints of I) Ag controllability, monodispersity of the obtained particles, and halogen composition. Formula Y=KX [wherein, X is the C11Br ratio (molar ratio) of the produced silver halide, and K is a positive number from 40 to 1200. Furthermore, the value of K is preferably within the range of the numerical value determined by the following formula, depending on the temperature of the emulsion mother liquor at which silver halide is formed and clouded. K= (634,9-12,75t+0.07938
t2)S Here, L is the temperature ('C) of the emulsion mother liquor at which silver halide is produced and suspended, and S is a positive number from 3 to 1/3. When producing an emulsion, the silver ion solution (first
A halide ion solution (second solution) is added so that the amount of halide ions is almost equal to the amount of silver ions in the pAg control solution. The concentration and/or addition rate is adjusted so that il! is sufficiently small. It is added as I. I) When the addition rate of the Ag control liquid is close to the addition rate of the second liquid, the concentration of the pAg control liquid is 1710% of the total halide ion concentration of the second liquid.
The concentration of halide ions in the second liquid is preferably equal to or less than 1,710, and if the addition rate can be set to 1710 or less of the WSZS hot liquid rate, it may be equal to the halide ion concentration of the second liquid. To control the above-mentioned addition rate, a commonly used flow rate control technique can be used. The preferred temperature for silver herodenide production in the present invention is 2
The temperature is 0 to 80°C, more preferably 30 to 70°C. Core-shell type grains and laminated type grains, which are preferably used as internal latent image type silver helodenide emulsion grains according to the present invention, are equivalent in that they consist of an inner core and at least one layer of outer shell covering the inner core as far as the cross section of the grain structure is concerned. However, in the core-shell type, the inner core has already matured as a photosensitive particle, whereas in the laminated type, the inner core is covered with an outer shell, and the photosensitive nucleus is formed at the interface due to crystal distortion or other factors. It is roughly distinguished as something that generates. However, even in the core-shell type, an fff layer type zero factor can be introduced by adjusting the silver halide composition of the core (inner core) and shell (outer shell), and the chemical ripening effect applied from the outer shell surface toward the inside. Alternatively, since the bleaching effect can be spread, in the present invention, unless carp meat is used, there is no sharp distinction between the two [referred to as core-shell type]. In addition, according to the present invention [She/L- of the core-shell type particles is 2
It may be a multilayer shell of jv1 or higher. The shell of the silver halide grains of the present invention may completely cover the surface of the silver halide core or inner shell, or
Alternatively, a portion of the surface may be selectively coated. In the present invention, the outermost shell layer preferably covers 10% or more of the particle surface.゛In the case of a multilayer shell in the present invention, the scraps adjacent to the outermost layer contain less silver chloride than the outermost layer, but this difference is at least 10 mol% or more based on the silver chloride composition ratio of the outermost layer. It is preferable to have a small silver chloride composition ratio. However, in the case of a laminated type, the difference in silver chloride composition between the core and shell averages is preferably 30 mol% or more. Any silver halide composition may be used as long as it satisfies these conditions. Examples include silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodide, and silver chloroiodobromide. The multilayer shell consists of at least an outermost layer and a layer adjacent thereto, but it may also have a structure in which layers having mutually different silver halide compositions are laminated, or in the radial direction of the silver halide grains, A structure in which the silver halide composition changes continuously may also be used. The multilayer shell in the silver halide grains of the present invention may be a multilayer shell consisting of more than two layers. The core of the [core/shell] type silver halide grains of the present invention preferably contains at least 50 mol% of silver bromide, and further contains silver chloride, V/or silver iodobromide. The silver halide grains forming the core may have any shape; for example, they may be cubic, octahedral, or a mixture thereof; they may also be spherical, tabular, irregular, etc. It may be a regular shaped particle. Although the average particle size and particle size distribution of the silver octalodenide grains constituting the core of the present invention can be varied widely depending on the desired photographic performance,
The narrower the particle size distribution, the more preferable it is. That is, the silver halide grains constituting the core of the present invention are preferably substantially monodisperse. The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times with an electron microscope and projecting the particles, and actually measuring the particle diameter or the area at the time of projection on the print (the number of particles measured is nil). Suppose there are more than 1,000 types of discrimination.) The method for producing the above-mentioned monodisperse core emulsion is, for example,
B-36890, JP-A-54-48520, JP-A-54
The double jet method disclosed in Japanese Patent Application No.-65521 and the like can be used. In addition, a premix method described in JP-A-54-158220 and the like may also be used. When producing a monodisperse emulsion by the method of the present invention, separately prepared fine silver halide crystals (so-called seed emulsion) are added in advance to a mother liquor containing a protective colloid, and then a tetrazaindene compound is added to the mother liquor. Preferably, an ammoniacal silver nitrate solution and a halide ion solution are added below to grow the seed emulsion grains to a desired grain size. There are no particular limitations on the conditions for preparing the seed emulsion used at this time. The core of the silver halide grain in the present invention is chemically sensitized or may be doped with metal ions.
Many methods are known for chemical sensitization. That is,
These sensitization methods include sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and a combination of these sensitization methods. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. Such methods are described, for example, in U.S. Pat. No. 1,574,944;
No. 623,499, No. 2゜410.689, No. 3,6
No. 56,955, etc. The core of the silver halide grains used in the present invention is, for example, US Pat.
As stated in No. 2゜642.361, etc.
Sensitization can be carried out with a water-soluble gold compound or with a reduction sensitizer. Such methods are described, for example, in U.S. Pat.
Reference can be made to the descriptions in No. 18,698, No. 2,983,610, etc. Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. Such methods are described, for example, in U.S. Pat.
8,060 and British Patent No. 618,061. The core of the silver halide grains in the present invention can be doped with metal ions. To dope the core with metal ions, the metal ions can be added as water-soluble salts, for example, during any process of forming the core particles. Preferred specific examples of metal ions include iridium,
There are metal ions such as lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions are preferably used in concentrations of 1X10-'' to IX10-' moles per mole of silver. The shells of the silver halide grains in the present invention are chemically sensitized or It is more preferable that the metal ion covers 50% or more of the surface area of the core doped with metal ions, and it is particularly preferable that the core is completely covered. ?) Two-piece method or premix method can be used.Fine-grained silver halide can also be mixed with the second emulsion and formed by Ostwald ripening. It is preferable that the silver grains RWJ are not chemically sensitized, or even if they are sensitized, the sensitization is only to a slight extent. When the surface of the silver halide grains of the present invention is chemically sensitized,
This can be carried out in the same manner as the chemical sensitization of the core particles. The silver halide grains used in the present invention preferably have a narrow grain distribution even after shell formation and are substantially monodisperse. That is, it is preferable that the silver halide grains as a whole are substantially monodisperse. Here, monodisperse silver halide grains as a whole are those in which the weight of silver halide contained within a grain size range of ±20% centering on the mode grain size rm is 60% or more of the total silver halide weight part. preferably 70% or more, particularly preferably 80% or more. The ratio of silver halide between the core and the shell of the present invention can be arbitrarily determined, but it is preferable that the ratio of the shell is 20% to 99% based on the total silver halide of the silver halide grains. In the composition ratio of the halogenated 111 grains of the present invention, the ratio of silver chloride in the grains as a whole is preferably 0 to 75 mol %. The meaning that the grain surfaces are not prefogged means that the emulsion used in the present invention is coated on a transparent film support with a thickness of 35 m
This means that the density obtained when a test piece coated with gAg of 7 cm2 is developed at 20°C for 10 minutes without exposure with the following surface developing liquid crystal does not exceed 0.6, preferably 0.4. Surface developer ^ Metol 2.5g! -Asfulvic acid 10゜NaBOz ・411t 0 35g
Add K13r 1g water II! Further, the silver halide emulsion according to the present invention can be prepared using internal developer B having the following formulation after exposing the test piece prepared as described above.
It gives sufficient density when developed with. Internal developer port
2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-water salt) 52.5g KBr
5gKr
O, 5g water added to 1gMore specifically, a portion of the specimen was exposed to a light intensity scale for a defined period of time up to about 1 second and developed at 20°C in an internal developer QB. a maximum of at least 5 times, preferably at least 10 times, when developed for 10 minutes, than that obtained when another portion of the specimen exposed under the same conditions is developed for 10 minutes at 20° C. with a surface-developed liquid crystal. It indicates the concentration. The silver halide emulsion according to the present invention can be optically sensitized using commonly used sensitizing dyes. Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative type silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. For information on sensitizing dyes, see Research Disclosure.
osure) No. 15162 and No. Reference may be made to No. 17643. The photographic light-sensitive material of the present invention is image exposed (photographed) by a conventional method.
After that, a bond image can be easily obtained directly by surface development. That is, the main step of directly creating a positive image is to apply the photographic light-sensitive material of the present invention having an internal latent image type silver halide emulsion layer that has not been fogged in advance by chemical action or optical fusing after image exposure. Kakoζ
The surface development process is carried out after a process that generates nucleation, that is, a fog process, and/or while carrying out a 'cross process. This can be carried out using a compound that generates a nucleus, that is, a fogging agent.In the present invention, the entire surface exposure is performed by immersing or moistening the image-exposed light-sensitive material in a developer or other aqueous solution, and then exposing the entire surface uniformly to light. The light source used here may be any light within the wavelength range to which the photographic light-sensitive material is sensitive, and high-intensity light such as flash light may be applied for a short period of time, or weak light may be used. The total exposure time can be varied over a wide range depending on the photographic material, development processing conditions, class S light source used, etc. in order to obtain the best final positive image. A wide variety of compounds can be used as the flashing agent used in the invention, and it is sufficient that the flashing agent is present during the development process. (particularly preferably in the silver halide emulsion layer), or may be included in the developing solution or J!l! solution prior to development processing.The amount used can be varied over a wide range depending on the purpose, and is a preferred addition. When added to a silver halide emulsion layer, the amount is 1 to 1500 B per mole of silver halide, preferably 1
It is 0 to 1000 yards. When added to a processing solution such as a developer, the preferred amount is 0.01 to 5 g/l, most preferably 0.05 to 1271 g/l. Fogging agents used in the present invention include, for example, U.S. Pat.
563,785, hydranones described in 2,588,982, or U.S. Patent No. 3,227.5
Hydrazide or hydrazone compounds described in US Pat. No. 52; US Pat. Nos. 3,615,615 and 3,718,47
No. 9, No. 3,719,494, No. 3,734,738
No. 4 and heterocycle No. 4 described in No. 3,759,901
Furthermore, there may be mentioned compounds having an adsorption group on the surface of silver halide, such as acylhydrazi/phenylthioureas described in US Pat. No. 4,030.925. Moreover, these fogging agents can also be used in combination. For example, research disclosure (Resea)
CH Disclosure No. 15162 describes the use of a non-adsorptive fogging agent in combination with an adsorption-type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, and they can also be used in combination. Specific examples of useful neutralizing agents include hydranone hydrochloride, phenylhydranone hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-methylphenyl)hydranone, 1-7 cetyl-2- Phenylhuman 2-syn, 1-7 cetyl-2-(4-7cetamido-7enyl)
Healanone, 1-methylsul-7-2-7-2-2-2-2-22-hydracn, 1-benzoyl-2-7-2-2-2-2-2-hydracn,
1-Methylsul7onilumidophenyl phenylhydrazine-formylethyl)-2-methylbenzothiazolium bromide, 3-(2-formylethyl)-2-propylbenzothiazolium bromide, 3-(2-acetyl) ethyl)-2-pencylbenzoselenazolium puromite, 3-(2-7 cetylethyl)-2-benzyl-5-7
Enylbenzoxazolitum bromide, 2-methyl-3-[3-(phenylhydradi])propyl]benzothiazolium bromide, 2-methyl-3-( 3-(
p-)lylhydranono)propyl]benzothiazolium bromide, 2-methyl-3-(3-(p-sulf77phenylhydrazino)propyl)benzothiazolium bromide, 2-methyl-3-(p-sulf 7ofenylhydrano)pentyl]benzothi, azolium iodide,
1,2-dihydro-3-methyl-4-phenylpyrido (
2.1-b) Benzothiazolium bromide, 1.2-
Dihydro-3-methyl-4-phenylpyrido (2.1
-b) -5-phenylbenzoxacilium bromide, 4,4'-ethylenebis(1,2-dihydro-3-
N-substituted m quaternary cycloammonium salts such as methylpyrido (2,1-b) benzothiazolium bromide) and 1,2-dihydro-3-methyl-4-phenylpyrido (2.1-b) benzoselenazolium bromide ;5-(1-
Ethylna7) (1.2-13)Thiazoline-2-y+)tenethylene)-1-(2-phenylcarbazoyl)methyl-3-(4-sulfamoylphenyl)-
2-Thiohyguntoin, 5-(3-ethyl-2-penzothiazolinylidene)-3-(4-(2-7ormylhydrac/)7enyl]rhodanine, i(4-(2-7
Examples thereof include olumylhydrazino)phenyl]3-phenylthiourea, 1,3-bis[4-(2-7 ormylhydrazino)phenyl]thiourea, and the like. After image exposure, the photographic light-sensitive material having a silver halide emulsion layer according to the present invention is exposed to light on its entire surface or in the presence of a fogging agent.
A positive image is directly formed by surface development. This surface development processing method means processing with a developer substantially free of silver halide solvent. Developers that can be used in the surface developer used for developing the photographic light-sensitive material according to the present invention include common silver halide developers, such as polyhydroxybenzenes such as hydroquinone, and amyl/7ethols. , 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylene aminoisos, etc., or mixtures thereof. Specifically, hydroquinone, amino/7er/-el, N
-Methylaminophenol, 1-phenyl-3-pyrazolidone, 1-722-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N , N-diethyl-1)-phenylenenoamine, diethylamine-
〇-) luidine, 4-7mi/-3-methyl-N-ethyl-N-(β-methanesul7onamidoethyl)aniline, 4-amine-3-methyl-N-ethyl-N-(β-hydroxy ethyl)7niline and the like. These developers are included in the emulsion in advance and are high p1 (
It is also possible to act on the silver halide during immersion in an aqueous solution. The developer used in the present invention can further contain specific anti-frigue agents and development inhibitors, or these developer additives can be optionally incorporated into the constituent layers of the photographic material. be. Depending on the purpose, various photographic additives such as wetting agents, film property improvers, and coating aids may be added to the silver halide emulsion according to the present invention. Examples of wetting agents include nohydroxyalkanes, and examples of film property improving agents include copolymers of alkyl 7-acrylates or alkyl methacrylates and 7-acrylic acid or methacrylic acid, and styrene-maleic acid copolymers. Water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as coalescence, styrene maleic anhydride bar 7 alkyl ester copolymer, etc. are suitable, and as coating aids, for example, saponin, polyethylene glycol lacryl ether, etc. are suitable. included. Other photographic additives include gelatin plasticizers, surfactants,
UV absorbers, pH adjusters, antioxidants, antistatic agents,
Thickeners, graininess improvers, dyes, mordants, brighteners, development rate regulators, matting agents, etc. can also be used. The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to form the internal latent image type silver helodenide photographic photosensitive material of the present invention. Get the materials. It is useful to apply the present invention to color photographic materials, in which case it is preferred to include cyan, magenta and yellow dye image-forming couplers in the silver halide emulsion. As the coupler, commonly used couplers can be used. In addition, it is useful to use ultraviolet absorbers such as thiazolidone, ben I triazole, acrylonitrile, and benzophenone compounds to prevent fading of dye images due to short-wavelength actinic rays.
It is advantageous to use Ciba 01 326, 327, and 328 (all manufactured by Ciba Iggy) alone or in combination. Examples of the support for the photographic material according to the present invention include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, lath, baryta paper, polyethylene laminate paper, etc., which have been pre-processed as necessary. can be mentioned. In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion layer according to the present invention, depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin. In addition, in the present invention, other hydrophilic bonds M (binder) can be included depending on the purpose, and colloidal albumin, agar, gum arabic, dextran, alginic acid, hydrolyzed to acetyl content of 19 to 20%. cellulose derivatives such as cellulose acetate, polyacrylic 7mide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinylalkone(-vinylaminoacetate copolymers), polyvinyl alcohol, These include polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated 7-sylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, poly7-ethyl methacrylate, polyethyleneamine, etc., and emulsions. Depending on the purpose, it can be added to constituent layers of photographic materials such as layers or intermediate layers, protective layers, filter layers, backing layers, etc.
Furthermore, the hydrophilic binder may contain a suitable plasticizer, wetting agent, etc. depending on the purpose. Further, the constituent layers of the photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent. These hardening agents include chromium salts, zirconiums, aldehydes such as 7-olmaldehyde and mucohalogen acids, halotriazine, polyepoxy compounds, ethyleneimine,
Examples include vinyl sulfone type and acryloyl type Dura Qiq. The photographic light-sensitive material according to the present invention has a photosensitive emulsion layer containing at least 1 frI of internal latent image type silver halide grains according to the present invention on a support, and also has a filter 1. Middle class, protect! It is possible to provide a number of different photographic Vt constituent layers, such as layers, subbing layers, backing layers, antihalation layers, etc. When the photographic material of the present invention is used for full color use, at least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one blue-sensitive silver halide emulsion layer are coated on the support. be done. At this time, it is sufficient that at least 1/li of the photosensitive silver halide emulsion layer contains the internal latent image type silver halide grains according to the present invention, but all the photosensitive halo and silver denide emulsion layers according to the present invention It is preferable that the silver halide particles contain internal latent image type silver halide grains according to the above. Furthermore, each light-sensitive silver halide emulsion layer may be the same color-sensitive layer or may be separated into two or more layers having different sensitivities. In this case, at least one layer having different sensitivities may be separated. - It is sufficient if the color-sensitive layer contains the internal latent image type silver halide grains according to the present invention, but it is preferable that all the emulsion layers contain the internal latent image type silver halide grains according to the present invention. The photographic light-sensitive material according to the present invention is suitable for general black and white use, for X-ray use,
For color, false color, printing, infrared layer, micro,
It can be effectively applied to various uses such as kite dye bleaching, and it can also be applied to colloid transfer method, silver salt diffusion transfer method, U.S. Patent No. 3,087,817 of Ronoyers, U.S. Pat.
No. 7 and No. 2,983,606, U.S. Pat. No. 3,253,915 to Weyertz et al., U.S. Pat.
No. 7,551, U.S. Pat. No. 3,227 to Whitemore et al.
No. 552 and U.S. Pat. Nos. 3,415,644, 3,415,645 and 3,415,646 to Land et al. .

【Effect of the invention】

By using the internal latent image type silver halide emulsion unique to the present invention, it is possible to obtain a silver halide photographic light-sensitive material with a sufficiently large maximum density, a sufficiently small minimum density, and high sensitivity with excellent storage stability. I can do it.

[Example 1] The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example-1 Using the five types of solutions shown below, silver chlorobromide emulsion EM-
1 was adjusted. The seed emulsion was a monodisperse silver chlorobromide emulsion with an average grain size of 0.27 μl. (Solution ^-1) Ossein gelatin 31.4. '
Distilled water 1285zt' polyisopropylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution
2.8ij! 28% ammonia water
18.9zt seed emulsion 0.
1287 mol equivalent (solution row 1) 8 g NO = 218. h
28% ammonia water Make 641.6i+1 with 182.1ml distilled water. (Solution C-1) Add 152.7g of KBr to 641.6z1 with distilled water. (Solution D-1) KDrl19. Aqueous solution containing O+v pAg adjustment required amount (solution E-1) 56% acetic acid aqueous solution +) HM adjustment amount required 40℃
JP 57-92523 and JP 57-92
Using the mixer shown in No. 524, solution B-1 and solution C-1 were added to solution ^-1 by a simultaneous mixing method over a period of time such that no particulates were generated. 1) Δg% pH and addition rate of solution B-1 during simultaneous mixing are shown in Table-
Control was performed as shown in 1. 1) Control of 8 g and pi was performed while changing the flow rates of solution D-1, solution E-1, and solution C-1 using a roller tube pump with variable flow rate. Two minutes after the addition of solution B-1 is completed, the pH is adjusted to 6.0 with solution E-1. ! I made 4 adjustments. Table 1 Next, wash with desalinated water in a conventional manner, and use Ossein Gelatin 3.
After dispersing in an aqueous solution containing 5.2 g, the total amount was reduced to 1 with distilled water.
000ij! It was prepared as follows. The obtained emulsion is designated as EH-1. Divide the E14-1 obtained above and add 1 silver to a part of it.
Sodium thiosulfate (pentahydrate) is 3.2 per mole.
13 was added and aged at 60°C for 70 minutes. The obtained emulsion was designated as EM-2. On the other hand, to another part of E14-1, 3.2 g of sodium thiosulfate (pentahydrate) and 0.96 II g of potassium chloroaurate were added per mole of silver, and chemical sensitization was performed at 60°C for 70 minutes. Ta. The obtained emulsion was designated as EM-3. EM-2 obtained above is used as a core emulsion as shown below.
Silver bromide core/shell type emulsion EM-4 using different solutions
was prepared. (Solution ^-4) Ossein gelatin 16.73i? Distilled water 96!5.6ml Polyisobrobylene-polyethyleneoxynosuccinate sodium salt 10% Ethanol solution 2.8x128%
Ammonia water 18.9111! Seed emulsion (EM-2) G, 5957 mol equivalent (solution B-4) 8 goos 138.8
fI28% ammonia water 115.8
Make it 408.1zII with ml distilled water (:f#
Liquid C-4) KBr 97.13
Make 408.1 zl with 1F distilled water (Solution D-4) Add 19.1 zl of KBr in 1000 zji of solution. Aqueous solution containing Og 9Ag adjustment required amount (solution RE-4) 56% acetic acid aqueous solution Wt I) 11 adjustment amount required At 40 ° C. Using this method, the solution@8-4 and the solution C-4 were added to the solution@8-4 by a simultaneous mixing method over a period of time such that no particulates were generated. The pAg-pH and the addition rate of Solution Row 4 during simultaneous mixing were controlled as shown in Table 2. 1) 8g and p
l+ was controlled by changing the flow rates of solution D-4, solution E-4, and solution C-4 using a roller tube pump with variable flow rate. Two minutes after the addition of solution It-4 was completed, p
H to 6.0 to 31! I arranged it. Table 2 Ossein gelatin 3
5.2. After dispersing in an aqueous solution containing
I tuned it to 000zl. The obtained emulsion was designated as EM-4. EM-5 was prepared in the same manner as EM-4. However, solution ^-5 was used instead of solution ^-4, and solution C-5 was used instead of solution C-4, and otherwise the same procedure as E14-4 was performed. (Soluble R, Go-5) Ossein gelatin 16.73g Distilled water
985.6ml polyisopropylene-polyethyleneoxy-nosuccinic acid ester sodium salt 10
% ethanol solution 2.8ml128% ammonia water 18.9z14-hydroxy-6-methyl-1,3,3a-tetraazaindene
84.4H seed emulsion (EM-2) 0
．． 5957 mol equivalent (solution C-5) KBr 97.13g4-hydroxy-6-methyl-1,3,3at7-tetraazaindene 115,619 408. Make it lzl. EM-6 was prepared in the same manner as EM-4. However ^-
Seed emulsion (E14-3) in an amount equivalent to 0.5957 mol was used in place of the seed emulsion (EM-2) in an amount equivalent to 0.5957 mol in CM-4, except that the same procedure as in CM-4 was conducted. EM-7 was prepared in the same manner as EM-5. However, instead of the seed emulsion (EM-2) in solution ^-5, an amount equivalent to 0.5957 mol, the seed emulsion (EM-3), 0.5957
The same procedure as EM-4 was performed except that molar equivalent amounts were used. The four emulsions obtained above EM-4, EM-5, EM-
6. Chemical sensitization was carried out at 50°C for 90 minutes by adding 2.2H sodium thiosulfate (pentahydrate) and 1,511F potassium chloroaurate per mole of silver to EM-7. Got 4! I! After adding a commonly used spreading agent and a hardening agent to each emulsion, the emulsion was coated on a cellulose triacetate support and dried to give a coating silver of 13511F/100CI'' to obtain Samples 1 to 4. Some of these coated samples were Temperature 27℃, relative humidity 60%
(condition-1) for 3 days, and another part was stored for 3 days at a temperature of 50° C. and a relative humidity of 80%. (Condition-2) These samples were exposed to light through an optical wedge for sensimetry using a sensitometer (hereinafter referred to as wedge exposure), developed for 4 minutes at 20°C with a developer with the following formulation, then washed with water, fixed, and washed with water. , and dried. Phenidone 0.4g Sodium sulfite (anhydrous) 75.0° Hydroquinone 10.0g Sodium carbonate (-hydrate) 40.09 Potassium bromide
4.095-Methylbenztriazole 10.0i+g1-formyl-2-phenylhydrazine (fogging agent) 0, ilF Add water 11 (adjusted to pH 12.5 with sodium hydroxide) Sensitivity, maximum for the resulting positive image Density (Dmax) Minimum density (Dmi
Table 3 shows the results of measuring n) and sensitivity. however,
The sensitivity was expressed as a relative value of the reciprocal of the exposure amount given the density of (Dmax+Dmin)/2. Table 3 From the results in Table 3, the emulsion of the present invention has high sensitivity and a sufficiently high maximum density, and even under high temperature and high humidity conditions, the decrease in maximum density, increase in minimum density, and sensitivity fluctuation are small. I understand that. Example-2 Silver chlorobromide emulsion EH-8 was prepared using the five types of solutions shown below.
The type 0 emulsion prepared by g is a monodisperse silver bromide emulsion with an average grain size of 0.
．． It is 27 μm. <TA liquid^-8) Ossein gelatin ao, sg distilled water
1258.6ml' Polyisopropylene-polyethylene oquine-succinic acid ester sodium salt 10% ethanol solution 2.811128%
Ammonia water 18.92xi' seed emulsion 0.1670 mol equivalent (solution B-
8) 8 gooz 211.6
g28% ammonia water 1 flow, 6ml
Make it 622.4i+1 with distilled water. (Solution C-8) 17.28 g of NaC 133.3 g of KDr Make up to 622.4 ml with distilled water (Solution D-8) [156.5 g of NaC and 4.0 g of KBr in 1000 tl]
Aqueous solution containing IIF DAg
Amount required for adjustment (solution E-8) 56% acetic acid aqueous solution B pH adjustment required 140
Ronioite VF Kaisho No. 5792523 and No. 57-9
Using the mixer shown in No. 2524, solution B-8 and solution B-8 were added to solution ^-8 by a simultaneous mixing method over a period of time such that no particulates were generated. pAg during simultaneous mixing
-The pH and addition rate of solution El-8 were controlled as shown in Table-4. pAg and pH were controlled by changing the flow rates of solution D-8, solution E-8, and solution C-8 using a roller tube pump with variable flow rates. Two minutes after the addition of solution B-8 was completed, the pH was adjusted using solution E-8.
．． 2. After dispersing in an aqueous solution containing
Adjusted to 00z1. The obtained emulsion is designated as EH-8. A silver chlorobromide emulsion EN-9 was prepared using the EN-8 obtained above as a core and the following four types of solutions. (Solution ^-9) Ossein gelatin 14.2g distilled water
904.3al polyisopropylene-polyethylene oxinosuccinic acid ester sodium salt 10% Polymer solution 2.8zi' seed emulsion (EM-8) 0.6849 mole equivalent (
Solution B-9) 8gNo.
Add 123.6g of distilled water to make 383.5ml. (Solution C-9) NaCj' 21.27
9KBr, 43.26
g to 363.51N with distilled water (solution @ D-9) Nacj258. Ig and KB
ro, an aqueous solution containing 8g p
At the required Ag adjustment amount of 60°C, JP-A-57-9252
Solution B-9 and fic-9 were added to solution ^-9 by simultaneous mixing method using the mixing stirring method shown in No. 3 and No. 57-92524, taking a sufficient amount of time to prevent the generation of fine particles during the process. . During the simultaneous mixing, the addition rates of -p++ and solution 11-9 were controlled as shown in Table 5. Control of p to B was performed while changing the flow rates of solution D-9 and solution C-9 using a roller tube pump with variable flow rate. Table 5 Next, wash with demineralized water in the usual manner, and use Ossein Gelatin 35.
．． 2. After dispersing in an aqueous solution containing
Adjusted to 00m/. The obtained emulsion was designated as EM-9. EI4-10 was prepared similarly to E14-9. however,
In addition to solution ^-9, solution ^-10 was used, and solution C-
In addition to 9, solution C-10 was used. Other than that EM-9
I did the same thing. (Solution ^-10) Ossein gelatin 14.2g distilled water
904.3zz! Polyisopropylene
Polyethyleneoxy-nosuccinic acid ester sodium salt 10% ethanol solution 2.8z (14-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 58.2g seed emulsion (EM-8)
0.6849 mole equivalent (Solution QC-10) NAC121,27°K [lr 43.26g4
-Hydroxy-6-methyl-1,3,3a,7-tetraazai, de-/
61.8B with distilled water
Adjust the pH to 363.5. Further, a silver chlorobromide emulsion E-11 was prepared using a solution of type 5191 shown below. The seed emulsion was a monodisperse silver bromide emulsion with an average grain size of 0.27 μl. (Solution ^-11) Ossein gelatin 28.87° Distilled water 1260.0 zl Polyisopropylene-polyethylene oxydisuccinate sodium, lithium salt 10% engineered tar solution
2.8itffi28% ammonia water
1B, 92 μl type 1 emulsion 0.1
670 mol equivalent amount (solution B-11) ΔgNOs
211.6g 28% ammonia water 17
6.6! Adjust the pH to 622.4 with distilled water. (Solution QC-11) Kl 2.07°Na
Cl30.9g KBr43.0g. Dilute to 622.4i+f with distilled water (solution D-1
1) NaCl38.411 and KBro in 1000xl solution
, 2y and aqueous WX pA
gll! i must (solution E-11) 56% acetic acid water soluble flag pH # adjustment required amount at 40°C
Solution B-11 and solution C-11 were added to solution ^-11 using a mixing stirrer shown in No. 24 by a simultaneous mixing method over a period of time such that no particulates were generated. The addition rates of pAg-pl+ and solution B-11 during simultaneous mixing were controlled as shown in Table 6. IjAg and pH were controlled using a roller tube pump with variable flow rate.
11 while changing the flow rates of solution E-11 and solution C-11. Two minutes after the addition of molten gt+-tt was completed, the pH was adjusted to 6.0 with solution E-11. Table 6 Next, wash with salt water using the usual method, and use Ossein Gelatin 35.
．． 2. After dispersing in an aqueous solution containing
711 was adjusted to 00z1. The obtained emulsion was designated as E-11. Using EM-11 obtained above as a core, silver chlorobromide emulsion EM-12 was prepared using the following four types of solutions.
Ml did. (Solution formula-12) Ossein gelatin 9.37° distilled water
F87.2M1 polyethylene propylene polyethylene oxydisuccinate sodium salt 10% ethanol FE liquid 2.8i+F type emulsion (EH-11) 0.8554 mole equivalent (solution 1)-12) 8g No.394.6g Distilled water So 278. 'lxl. (Solution C-12) NaC13.26g K[lr 59.6g with distilled water 278.2zz! (Solution D-12) Solution 1000zz! Inside is NaCl35.3g and KBr6
．． Aqueous solution containing 5y pAg adjustment required amount At 60 ° C., using a mixing stirrer shown in JP-A-57-92523 and JP-A-57-92524, solution formula-12 and solution Ic-12 were simultaneously added to solution formula-12. The mixing method required time for the addition so that no fine particles were generated during the addition. The addition rate of pAg"pHB and solution B-12 during simultaneous mixing was controlled by i#1 as shown in fi-7.I)Ag and I]H were controlled by a roller tube pump with variable flow rate. and solution C-12
This was done while changing the flow rate. Table 7 Next, wash with desalinated water in a conventional manner and use Ossein Gelatin 35.
．． After dispersing in an aqueous solution containing 2 g, the total amount is reduced to 10 with distilled water.
00*j! Adjusted to. The obtained emulsion is designated as EH-12. Separately, silver chlorobromide emulsion EM-13 was prepared using five types of solutions shown below. The seed emulsion was a monodisperse silver bromide emulsion with 0.27 micron particles. (Solution ^-13) Ossein gelatin 28.87y Distilled water 1200. OzN polyisopropylene-polyethyleneoxydisuccinate sodium salt 10% ethanol solution 2.8z14-human axy-6-methyl-1,3,3m,7-tetraazaindene 9.5 Cucarium hexalochloroiridate 18 (Solution C-13) Kl 2.07°Na
(J
50.9gKDr
43.0g4-hydroxy-6-methyl-1,3,3m,7-chitra7zaindene
70.5 mg distilled water to make 622.4 liters (solution D-13) NaCl38.42 and KBr in solution 1000i+4
, 2g, pA
g Adjustment required amount (solution E-13) 56% acetic acid aqueous solution w1 pH adjustment required amount at 40°C
- Using the mixer shown in No. 92524, the solution ^-
Solution B-13 and solution C-13 were added to No. 13 by a simultaneous mixing method over a period of time such that no fine particles were generated. The pAg-pH and the addition rate of solution B-13 during simultaneous mixing were controlled as shown in Table 8. j) Ag and p
l+ was controlled by changing the flow rates of solution ox3m solution E-13 and solution C-13 using a roller tube pump with variable flow rate. Two minutes after the addition of solution B-13 is completed, Qp is added to solution E-13.
H was adjusted to 6.0. Table 8 Next, wash with desalinated water in a conventional manner and use Ossein Gelatin 35.
,2. After dispersing in an aqueous solution containing
00zz! Adjusted to. The obtained emulsion was designated as EM-13. Using the E-13 obtained above as a core, silver chlorobromide emulsion EM-14 was prepared using the four types of solutions shown below. 4 were made. (Solution Δ-14) Ossein gelatin 9.37g distilled water
787.2ml polyisopropylene-polyethyleneoxydisuccinate sodium salt 10% ethanol solution 2.8i14-hydroxy-6-methyl-1,3,3n,7-tetrazaindene 38.3mg seed emulsion (EM-13
) 0.8554 mol equivalent (solution row 1
4) 8gNO* 94. (3
g Add distilled water to 278,2xe. (Soluble Ic-14) NaCj! 3.261
FK [lr 59.62
4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 23.7 g in distilled water
278.2ij! (Solution [D-14) 1/8 liquid 1000zz! 35.3g of NaCl and D
Aqueous solution containing r6.5g pA
g adjustment required amount At 60°C, dissolve QB-14 and solution C-14 in solution ^-14 by simultaneous mixing method using a mixing stirrer shown in JP-A-57-92523 and JP-A-57-92524. The addition took a long time to ensure that no fine particles were generated. The addition rate of pAg and solution 14 during simultaneous mixing is shown in Table-
Control was performed as shown in 9. pAg was controlled by a roller tube pump with variable flow rate.
-14 while changing the flow rate. Table 9 Next, wash with demineralized water in the usual manner, and use Ossein Gelatin 35.
．． 2. After dispersing in an aqueous solution containing
Adjusted to 00i+4. The obtained emulsion was designated as EM-14. EM-9, EM-10, EM-12, E obtained above
Sensitizing dyes represented by the following formulas were added to four types of emulsions M-14. In addition, the magenta coupler 1-(2,4,6-)lichlorophenyl)-3-(2-chloro-5-octadecylsuccinimide 7-nilino)-5-pyrazolone was dissolved in butyl 7-talate and ethyl acetate, and a gelatin aqueous solution was prepared. An emulsifier dispersed in Next, this emulsified dispersion was added to each of the above emulsions and mixed, and a hardener was added to achieve a coating silver amount of 6. Samples 5 to 8 were obtained by coating on a resin-coated paper support to give a ratio of 2 g/100 cI2 and drying. In addition, to EH-9, the above coupler emulsified dispersion was separately added, and 50 wg of 4-hydroxy-6-methyl-1,3°3a,7-tetraazaindene was added per mole of silver.
, 100H1200B and 400g of each, a hardening agent was added, and samples which were coated and dried in the same manner were also added to obtain Samples 9 to 12. These samples were exposed to light through a yellow filter and developed at 30° C. for 3 minutes with a developer having the following formulation. 4-7mi/-3-methyl-N-ethyl-N-(β-methanesul7onamidoethyl) aniline sulfate 5.0 g Sodium sulfite (anhydrous) 2.0° Sodium carbonate (-hydrate) 15. O. Potassium bromide 1.0g Benzyl alcohol 1011 Add water
11 (pH 10.2 with sodium hydroxide)
However, starting from 20 seconds after the start of development, the entire surface was uniformly exposed to white light of 0.6 lux for 20 seconds, followed by washing with water, bleaching, fixing, washing with water, and drying. (Dokoro J!
1-1) Processing-2 and Processing-3 were performed in the same manner as Processing-1. However, instead of uniformly exposing the entire surface with white light of 0.6 lux as in Process-1, the entire surface was uniformly exposed with white light of 0.3 Lux (Processing-2) and 0.15 Lux (Processing-3). - exposed to light. Table for the samples obtained in the above treatment-1 to treatment-3
As can be seen from the results in Section 10, samples of the emulsion of the present invention can yield good images with sufficiently large maximum densities and small minimum densities, and are stable against fluctuations in illuminance during full-surface exposure. I understand. It can also be seen that even if the 7zaindene compound is present during coating, the effects of the present invention cannot be obtained.

Claims (1)

[Scope of Claims] A silver halide emulsion layer having at least one silver halide emulsion layer containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance, and after image exposure, after fogging treatment, and/or
Alternatively, in a photographic light-sensitive material in which a positive image can be obtained directly by surface development while being subjected to a fogging process, at least a part of the internal latent image type silver halide grain structure is a novel halogen formed by mixing an ammine silver complex salt and a soluble halide. The structure of the internal latent image type silver halide grains that have passed through the growth process due to silver oxide precipitation is represented by the following general formula (I), (
II), (III), or (IV) and a compound having a repeating unit represented by the following general formula (V). Direct positive silver halide photographic material. General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2 and R_3 may be the same or different, and are hydrogen atoms, halogen atoms, Hydroxyl group, amino group, derivative of amino group, alkyl group, derivative of alkyl group, aryl group, derivative of aryl group, cycloalkyl group, derivative of cycloalkyl group, mercapto group, derivative of mercapto group or -CONH-
R_4 (R_4 is a hydrogen atom, an alkyl group, an amino group, a derivative of an alkyl group, a derivative of an amino group, a halogen atom,
Represents a cycloalkyl group, a cycloalkyl group derivative, an aryl group, or an aryl group derivative. ),
R_1 and R_2 may be combined to form a ring, and R_5
represents a hydrogen atom or an alkyl group, and X represents the general formula (I
), (II), (III) or (IV) from which one hydrogen atom has been removed, and J represents a divalent linking group. ]