JPS62186251A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having high max. optical density and low min. optical density, and a good shelf life and capable of a rapid processing by comprising an internal latent image type silver halide particle having a crystalline surface defined with Miller index (nn1) (n>=2). CONSTITUTION:The internal latent image type silver halide particle has the crystalline surface defined with Miller index (nn1) (n>=2). The composition of silver halide is not specified, and preferably is silver chloride, silver chlorobromide, silver iodobromide, silver bromide or silver chloroiodobromide. The particle constitution is preferably a core shell type emulsion. The core is preferably effected chemical sensitization and/or a doping with a polyvalent metal. The substrate of the shell can be controlled the characteristics thereof by effecting somewhat chemical sensitization.

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 positive image can be obtained.

[Conventional technology]

Conventionally known methods for obtaining direct positive images are mainly divided into two types. One type is to use a silver halide emulsion that has fog nuclei in advance, and to destroy the fog nuclei or latent image in exposed areas using solarization or the Burschel effect.
A positive image is obtained after development. The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and performs Jζ-curing treatment (development nucleation treatment) after image exposure, and then performs surface development, or after image exposure. A positive image can be obtained by performing surface development while performing fogging treatment (development nucleation treatment). It can be done chemically using a sharpening agent, or it can be done 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 (and is suitable for applications requiring high sensitivity) than the former type of method. Various techniques are known in this technical field.For example, silver halide emulsions of this type are described in U.S. Pat.
No. 34213, No. 58-1412 and No. 58-141
Comparts thin type, core shell type or 8N/I for No. 5 etc.
Thioethers, imidazole, and the like are described as particle growth agents in US Pat. Furthermore, U.S. Patent No. 3,761,267, U.S. Patent No. 3,206.3
No. 13 discloses a core-shell emulsion internally chemically sensitized or doped with a polyvalent metal, and JP-A-52-34213 discloses surface chemical development of emulsion grains occluding dopants.

[Problems to be Solved by the Invention] Photographic materials that form blurred images can be produced using these known techniques, but in order to apply these photographic materials to various photographic fields, Further improvement of photographic performance is desired. 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. 6,313. 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, and on the other hand, if grain growth agents such as 1,000-onythyl, 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 can be rapidly processed. [Means for solving the problem] In accordance with the purpose of the present invention, we have investigated silver halide crystals and found that at least one silver halide grain containing an internal latent image type silver halide grain whose grain surface is not fogged in advance. In a photographic light-sensitive material having one silver halide emulsion layer, a blurred image can be obtained directly by surface development after image exposure, after fogging treatment, and/or while performing fogging treatment, the internal latent image is The object of the present invention is solved by a direct positive silver halide photographic light-sensitive material characterized in that type silver halide grains have a crystal plane defined by a Miller index (uni) (where 11≧2). In the above embodiments of the present invention, the silver halide composition is not particularly limited, and may include silver chloride, silver chlorobromide, silver iodobromide, silver bromide, silver chloroiodobromide. is preferable, and a core-shell type emulsion is preferable as the grain structure. The core is preferably chemically sensitized and/or doped with a polyvalent metal. Further, the characteristics can be adjusted by slightly chemically sensitizing the surface of the shell. Note that chemical sensitization of the shell surface is not necessarily required. In addition to the crystal plane defined by the Miller index (nn1) (where n≧2), the particle has a (100) plane or a (100) plane and a
1) Particles having both surfaces may also be used. Further, the particle size is 0.1 to 3μ11, preferably 0.2 to 2μ.
0 layer volume, and more preferably 0.3 to 1.5 μl. Moreover, it is preferable that it is monodisperse. It is preferable that these monodispersed emulsions are appropriately mixed or formed into one ff layer for use in adjusting the gradation. First, silver halide grains having (n o 1 ) planes as used in the present invention will be explained. The mi diagram is a diagram showing the morphology of the entire silver halide crystal when the outer surface is made up of only (nnl) crystal planes. Moreover, FIG. 2 is a side view seen from the direction of straight lines b, , I) 2 of the ptSi diagram. There are 24 equivalent crystal planes expressed as (nnl) crystal planes. Therefore, a crystal in which all three outer surfaces are composed of (old 11) crystal planes takes the form of a 24-hedron, and each plane forming the outer surface is an obtuse triangle. There are two types of vertices. That is, the first
In the figure, there are six vertices equivalent to a, and eight vertices equivalent to a. At the vertex a1, 8 planes are in contact, and the vertex S,
In this case, three planes are in contact with each other. There are also two types of edges. That is, 24 sides C3 equivalent to sides a and b in FIG. 1, and 12 sides C2 equivalent to sides a and a2.
It is. Next, using cross-sectional views, (old 11) plane, (111) plane, (1
10) Explain the relationship between surfaces. Including straight lines S and b of the icosahedron in Figure 1, triangle a+a2b+ and triangle a1a2b
A cross-sectional view along plane d perpendicular to 2 is indicated by solid line 1 in FIG. 13. That is, in FIG. 3, real #X1 is connected to plane d and (
represents the line of intersection with the nnl) plane. On the other hand, break #X2 is (
110) plane, -fish+i13 represents the (111) plane, and the directions of the (old 11) plane, (110) plane, and (111) plane are indicated by normal vectors p, q, and ``, respectively. That is, P = (nnl) (n is a natural number, n≧2), q
= (110) and r= (111). θ is the angle formed by two (old 11) crystal planes adjacent to each other with the side ala2 as the boundary, and θ≧2.11 is 110° and θ<180° due to the restriction that 11 is a natural number. In other words, the (nnl) plane intersects two of the three crystal axes equidistant from the origin, and intersects the remaining one axis not parallel but at a slight inclination, so it can first be expressed as (111/11). Therefore, it is displayed as (nnl). As described above, the (n n 1 ) crystal plane according to the present invention is the ( n n 1 ) crystal plane that has been conventionally known in silver halide microcrystals.
It is clear that the 111) crystal plane and the (110) crystal plane are completely different crystal planes. Also, the fact that it is different from the (100) crystal plane does not require any particular explanation. On the other hand, Japanese Patent Application No. 59-206765 discloses "silver iodobromide grains having a J(110) crystal plane with a medium edge." In the Book of Light Is, this crystal plane is named the quasi-(110) plane, and is referred to as “two roof-shaped crystal planes that share a ridgeline.
The angle formed by the two quasi-(110) planes is more obtuse than 110°. ” is stated. In other words, the quasi-(110) plane refers to the (++nl) crystal plane (n≧2, n is synonymous with a natural number) according to the present invention. The silver halide grains according to the present invention have all outer surfaces formed in the (nnl) plane. , i.e. (11
1) plane, (100) plane, or (110) plane may exist. Examples of these are shown in FIGS. 4 to 11. (111) and (100) planes coexist, resulting in a 30-hedron (Figs. 5 and 8), a 38-hedron (Fig. 6.7), and a 32-hedron.
It takes the form of a facepiece (Figure 4). Furthermore, the monodispersity referred to in the present invention refers to the surface area "2 and The body 11 r' involved in the existence density of the base point of the photographic effect is the particle size r
We focused on the fact that the characteristics of the photographic emulsion containing the grains are predominantly determined by the multiplicative product nr' with the number n of grains having As a representative value that effectively represents the characteristics, the horizontal axis represents the numerator i of each particle, and the vertical axis represents the volume 1 month of the frequency n of that classification.
The weight given to i is the frequency n i r ',
The weighting based on i is applied to the frequency curve based on the mode of the statistical value, which is generally statistically defined by the maximum frequency of the frequency curve. I took it. In the present invention, monodispersity is defined when 60% or more of the total amount of silver halide grains Il is contained within a grain size ri with a grain size deviation of ±20% centered on mode r- as defined above. . In the present invention, the monodispersity is 70% or more, preferably 80% or more. When controlling the crystalline phase of the silver halide grains according to the present invention, silver halide grains are formed by mixing an ammoniacal silver nitrate solution or a silver nitrate solution and a halide ion solution in the presence of a protective colloid. , and the formation and growth of the silver halide grains are performed according to the following general formula (1), (I
Most preferably, the method is carried out in the presence of at least one compound selected from the compounds represented by f), (II) or (■) and the compound having a repeating unit represented by the following general formula (V). General formula (1) General formula (II) General formula (I
ll) General formula (IV) General formula (V) s (C112-C) In the formula, I'(,, R, and R3 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an amide 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 norcapto group or -CONII-
L (R represents a hydrogen atom, a furkyl group, an amine group, an alkyl group derivative, an amine/group derivative, a halogen atom, a cycloalkyl group, a cycloalkyl group derivative, an aryl group, or an aryl group derivative, ), R1
and R2 may be combined to form a ring, R1 represents a hydrogen atom or an alkyl group, and X represents the general formula CI), (II
). Water'l from the compound represented by (III) or (IV)
l: represents a monovalent group excluding one atom, and J represents a divalent linking group. In the general formulas (I) to (V), the furkyl group represented by R1-R4 includes, for example, a methyl group, an ethyl group, a propyl group, a pentyl group, a hekynyl group, an octyl group,
Isopropyl group, 5ee-butyl group, -butyl group, 2
- carbonyl group, etc., and examples of alkyl group derivatives include, for example, aromatic residue-substituted (divalent linking group,
For example, -NHCO-, etc. may be used) alkyl group (for example, benzyl group, phenethyl group, benzhydryl group, l
-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkyl groups substituted with alkoxy groups (e.g. methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxyethyl group, etc.) ), a halogen atom, a hydroxy group, a carboxy group, a mercapto group, an alkoxycarbonyl group, or an alkyl group substituted with a substituted or unsubstituted amino group (e.g., a monochloromethyl group, a hydroxymethyl group, a 3-hydroxyldyl group, a carboxyltyl group) , 2-carboxyethyl group, 2-(methoxycarbonyl)ethyl group, amitumedel group, diethylaminomethyl group, etc.), alkyl group substituted with dichloroalkyl group (e.g. cyclopendelmethyl group, etc.), the above general formula (1) Examples include alkyl groups substituted with monovalent groups obtained by removing one hydrogen atom from the compounds represented by ~(ff). Examples of the aryl group represented by It1 to R4 include phenyl group, ■-naphdyl group, etc., and examples of derivatives of the aryl group include p-)lyl group, ugly-ethylphenyl group, --cumenyl group, Mesityl group, 2.3-xylyl group, p-chlorophenyl group, 0-bromophenyl group, p-hydroxyphenyl group, 1-hydroxy-2-
Naphthyl group, p-methoxyphenyl group, p-methoxyphenyl group, p-carboxyphenyl group, O(methoxycarbonyl)phenylene group, s+-c ethoxycarbonyl)phenyl group, 4-carboxy-1- Examples include naphthyl group. Examples of the cycloalkyl group represented by R4 include a cycloheptyl group, a cyclopentyl group, a cyclohexyl group, and examples of derivatives of the cycloalkyl group include a methylcyclohexyl group. Examples of halogen atoms represented include fluorine, chlorine, bromine, and iodine; examples of derivatives of amino groups represented by R3-R4 include butylamino group,
Examples include diethylamino group and anilino group. R8-
Examples of the mercapto group derivative represented by R5 include methylthio group, ethylthio group, and phenylthio group. The alkyl group represented by rt s preferably has 1 to G carbon atoms, and includes, for example, a methyl group and an ethyl group. Especially preferred as Rb are 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-11) is preferred. (,y-1) (J-II)R@ In the formula, Y represents 10- or -N- (here, Ro 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 ethyl bond may be present between the alkylene groups. For example, a methylene group, an ethylene group, a propylene group, -CIl, 0C
11,-,-CIItCON)ICII,-,-C1
l, CII*C00CIIz, CHyCIIt
OCOCHt, CIIJIIICOCHt-, etc.)
-〇-alkylene group, -CONII-alkylene group, -
000-alkylene group, -0CO-alkylene group, and -NIICO-alkylene group (these alkylene groups preferably have up to 10 carbon atoms) or arylene group (preferably one having 6 to 12 carbon atoms; for example, p-phenylene) (such as a group). Particularly preferable divalent linking groups as J include the following. -CONIIC11, -, -CONIICH and CIlg
-, -CONIICIl, OCOCIIm-. C0NIICIIzCII*CIItOCOC11g
, C00(Jlt, C00CII*CIIt
. C00CH*CHtOCOCII*, C00CH
tCHtCHtOCO (Jlt. The compound having the unit represented by the general formula (V) may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, methacrylamide, acrylic ester, methacryl ester, etc. Next, a compound represented by the general formula (1), (II), (m) or (■) or a compound having a repeating unit represented by the general formula (V) (hereinafter referred to as a specific tetrazaindene compound) (3,) (4) Ura n+1 11+1 il y: 5 to 50 mol% copolymer IH y: 5 to 50 mol% copolymer υ11 y: 5 ~50 mol% of the copolymer Y: 5~50 mol% of the copolymer The specific tetrazaindene compound of the above compound according to the present invention is pre-existing in the mother liquor during the formation of the silver halide emulsion,
Further, it is preferable to increase the amount added as silver halide grains are produced and grow. Therefore, specific tetrazaindene compounds can be used in emulsion mixing mother liquors and halide ion solutions.
(hereinafter referred to as a halide solution) or a silver-containing ion solution.Also, a specific tetrazaindene compound solution is prepared separately from the above solution, and added to an emulsion together with a halide solution and/or a nitrate silver-containing ion solution. Injection is also a preferable method, but in practical terms, it is most preferable to mix it by adding it to the Ronin 1 halide solution in order to simplify the process and increase productivity. By changing the amount of the mixed mother liquor and the specific tetrazaindene supplied during silver halide grain growth, it is possible to control the history of the crystal phase during silver halide crystal growth and the shape (crystal habit) of the final grains. can. The amount of the specific tetrazaindene compound added varies depending on the grain size of the silver halide grains to be obtained, the composition of the halogen formal wear, the temperature during emulsion preparation, and the gI production conditions such as p II and 9Ag, but the amount of halogen produced 10 per mole of silveride
A range of -5 to 2X 10-' moles is preferred. In addition, when the specific tetrazaindene compound is a compound having a unit represented by the general formula (V), the amount added is determined by the number of moles of the tetrazaindene moiety. The method for producing the above-mentioned monodisperse core emulsion is, for example,
No. 8-38890, JP-A-54-48520, JP-A No. 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. The core of the core-shell type silver halide grains in the present invention may be chemically sensitized or doped with metal ions. Many methods are known for chemical sensitization. That is, sensitization methods include sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and combinations of these sensitization methods. As the sulfur sensitizer, 1000 sulfates, 1000 urea salts, thiazoles, rhodanines, and other compounds can be used. . Such methods are described, for example, in U.S. Pat. No. 1,574,9
No. 44, 1. (No. 323,499, No. 2,410,6
No. 89, No. 3, No. 656, No. 955, etc. The core of the silver halide grains used in the present invention is, for example, US Pat. No. 2,399,083, US Pat.
As stated in No. 2゜642.361, etc.
It is also possible to sensitize with a water-soluble gold compound, and it is also possible to sensitize 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 a method is described, for example, in U.S. Pat.
Reference may be made to the descriptions in No. 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, they can be added as a water-soluble salt of the metal ion, either during the formation of the core particle. There are metal ions such as bismuth, gold, osmium, and rhodium. These metal ions are preferably IX 1G'-''-IX 1G per mole of silver.
−' used in molar concentrations. It is more preferable that the shell of the silver halide grain in the present invention covers 50% or more of the surface area of the core which is chemically sensitized or doped with metal ions; . Particularly preferred is one that completely covers the area. As a method for forming the shell, the double jet method or premix method described above can be used. Alternatively, the core emulsion can be formed by mixing fine grains of silver halide and performing Ostwald ripening. It is preferable that the silver halide grains of the present invention are not chemically sensitized on the surface of the grains, or are sensitized only to a small extent. When chemically sensitizing the surface of the silver halide grains of the present invention,
This can be carried out in the same manner as the chemical sensitization of the core particles. The silver halide grains in the present invention preferably have a narrow grain distribution and are substantially monodisperse even after shell formation, that is, the silver halide grains as a whole are preferably substantially monodisperse. , IIt dispersibility is 70% or more, particularly preferably 80% or more. In the core-shell type grains of the present invention, the ratio of silver halide between the core and the shell can be arbitrarily determined, but the ratio of the shell to the total silver halide of the silver halide grains is 20% based on the total silver halide of the silver halide grains.
% to 99%. The composition ratio of the silver halide grains of the present invention can be selected from the range of 0% to 100% by mole of silver chloride in the grains as a whole. It may also contain silver iodide, the content of which is 0 to 10
Mol% is preferred. The silver halide grains of the present invention are supplemented with at least two layers having mutually different halogen compositions.
This type of emulsion, preferably i11, also consists of an inner core and an outer grain, and can be considered as one of the core/shell structures. Further, the internal latent image type silver helodenide grains of the present invention may be composed of three or more types of layers. The silver halide composition of the core is a chloride-containing IF smaller than the silver chloride content of the shell. The shape of the grain forming the core, which preferably consists primarily of silver bromide and may contain not more than 70% silver chloride, and may contain up to 15% silver iodide, can be any shape. For example, it may be a cubic crystal, a regular octahedron, or a mixture thereof, or may be spherical, tabular, or amorphous. It may be different, but preferably the silver chloride content of the shell is the same as the silver chloride content of the core! 10 mol% or more of pith, preferably
It is preferable that C< is larger by 20% by mole, more preferably by 30% by mole or more. The shell can completely cover the core or selectively cover a portion of the core. The meaning that the grain surfaces are not prefogged means that the emulsion used in this invention is coated on a transparent film support with 35+
This means that the density obtained when a test piece coated to give a density of 0.6 gAg/cm" is developed for 10 minutes at 20°C with the following surface developer without exposure to light does not exceed 0.6, preferably 0.4. Surface developer ^ Metol 2.5g 1-7 Scorbic acid 10゜NaBOz ・411z 0 8"1 for 35g
g Add water.
It gives sufficient density when developed with. Internal developer B Metol 2° Sodium sulfite (anhydrous) 90° Hydroquinone Sodium carbonate (-water salt) 52.5° Kflr
5゜Kl
□, 5° of water was added. when developed for 10 minutes at 20°C, at least 5 times, preferably 10 times, that obtained when another part of the specimen exposed under the same conditions was developed for 10 minutes at 20°C with a surface-developed liquid crystal. This indicates the maximum concentration. The silver halide emulsion according to the present invention can be optically sensitized using commonly used sensitizing dyes. Combinations of sensitizing dyes suitable for supersensitization, such as internal latent image type silver halide emulsions and negative-working silver halide emulsions, are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, see Research Disclosure.
closure) 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 blurred image can be easily obtained directly by surface development. That is, the main step of directly creating a positive image is to apply a photographic light-sensitive material having an internal latent image type silver halide emulsion layer that has not been previously coated according to the present invention to a chemical action or an optical action after image exposure. It consists of performing surface development after performing a process for generating thickened nuclei, that is, after performing a 3ζ process and while performing a 3ζ process. Here, the Jζ treatment is a compound that gives full exposure or generates fog nuclei, ie.
This can be done using a sizing agent. In the present invention, the entire surface exposure is completed by immersing or moistening the imagewise exposed photosensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface. The light source used here may be any light within the wavelength range to which the photographic light-sensitive material is sensitive; it can also be exposed to high-intensity light such as flash light for a short period of time, or it can be exposed to weak light for a long period of time. Also, the total exposure time depends on the photographic material, processing conditions, and light source used. ¥? This allows for a wide range of changes to be made in order to finally obtain the best blurred image. In the present invention, a compound having a wide range of aJ can be used as the 1: lubricating agent, and the lubricating agent only needs to be present during the development process. In the constituent layers (among them, the silver halide emulsion layer is preferable)6, or in the developer or the place prior to the development process J! I! May be included in the liquid 1.4: The amount used can vary widely depending on the purpose,
The preferred addition amount is 1 to 1,500 B, preferably 10 to 1,000 B per mole of silver halide when added to a silver halide emulsion layer. In addition, when added to a processing solution such as a developer, the preferable amount of addition is 0.01 to 5
g/l, particularly preferably from 0.05 to 1 g/l. Examples of Iζ-reducing agents used in the present invention include hydrazines described in U.S. Pat. No. 2,563,785 and U.S. Pat.
27,552; U.S. Pat. No. 3,815. f315, fq3,
No. 718.479, No. 3,719,494, No. 3. Biplane electric quaternary nitrogen salt compounds described in U.S. Pat. No. 34,738 and U.S. Pat. No. 3,759,901;
Compounds having an adsorption group on the silver halide surface, such as acylhydrazinophenylthio RZ described in No. 925, can be mentioned. These fogging agents can also be used in combination. For example, Research Disclosure (
Research Disclosure) No. 151
No. 62 describes the use of a non-adsorption type antifogging 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, or a combination of both can be used. Specific examples of useful curling agents include hydrazine hydrochloride, phenylhydranone hydrochloride, 4-methylphenylhydrazine hydrochloride, l-formyl-2-(4-methylphenyl)hydrazine, 1-7 cetyl-2 -Phenylhydrazine, 1-7cetyl-2-(4-7cetamido-7enyl)
hydrazine, 1-7tylsul-7onyl-2-7enylhydrazine, 1-benzoyl-2-phenylhydrazine,
Tomethylsulfunyl-2-(3-phenylsul7onamidophenyl)hydracune, 7olmaldehyde phenylhydrazine-formylethyl)-2-/thylbenzothiazolium bromide, 3-(2-formylethyl)-2 -Propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benclebenzoselenazolium bromide, 3-(2-acetylethyl)-2-pencyl-5-phenyl-benzooxacillium Bromide, 2
-/thiru-3-[3-(7znylhydrano/)propyl]benzothiazolium bromide, 2-methyl-3-(
3-(p-Tolylhydract)propyl]benzothiazolium bromide, 2-methyl-3-(3-(p-
sulf7aphenylhydranono)propyl]benzothiazolium bromide, 2-methyl-3-Cp-sulft7
x nylhydro-2-synbenthyl] pennthiazolium iode r, 1,2-hydro-3-methyl-4-7enylpyrido(2,1-1))benzothiazolium bromide,
1.2-dihydro-3-methyl-4-phenylpyrido (
2,ib)-5-phenylbenzoxacilium bromide, 4,4'-ethylenebis(1,2-dihydro-3!methylpyrido(2.1-b)benzothiazolium bromide), 1,2-dihydro -3-Methyl-4-phenylpyrido (2.1-b) N-substituted quaternary ammonium salt such as penzoselenazolium bromide: 5-
(1-ethylna7) (1,2-b)thiazoline-2
-i')r-ethylidene)-1-(2-7enylcarbazoyl)methyl-3-(4-sulf77moylphenyl)
-2-Thiohyguntoin, 5-(3-ethyl-2-penzothiazolinylidene)-3-[4-(2-7ormylhydranono)7enyl]rogenine, 1-(4-(2 -7
olumylhydrano)phenyl]3-phenylthiourea, 1.3-bis[4-(:”7tlumylhydranono)
Examples include phenylcothiourea. After the image exposure of the photographic light-sensitive material having a silver halide emulsion layer according to the present invention, a blurred image is formed directly by exposing the entire surface to light or by subjecting it to surface development treatment in the presence of wax. The method means processing with a developer that does not substantially contain a silver halide solvent.As the developer that can be used in the surface developer used for developing the photographic light-sensitive material according to the present invention, ordinary developers can be used. Silver halide developers include, for example, polyhydroxybenzenes such as hydroquinone, amino 7-ethers, 1,3-pyrazolidones, ascorbic acid and its derivatives, legectones, 7-enylenenoamine M, etc., or mixtures thereof. Hydroquinone, amino 7-ethyl, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 17xnyl-4-methyl-4-hydroxy Methyl-3-pyrazolidone, ascorbic acid, N, todiethyl-p-7znireshi')7mine, quethylamine-〇-toluinone, 4-7mi/-3-methyl-N-dityl-N-(β-methanesul7oneamide) ethyl)aniline, 4-amine-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline, etc. These developers are included in the emulsion in advance and are
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 antifoggants and development inhibitors, or these developer additives can be optionally incorporated into the dead layer 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 dihydroxyalkanes, and examples of film property improving agents include copolymers of alkyl acrylates or alkyl methacrylates and acrylic acid or tactacrylic acid, styrene-maleic acid copolymers, and styrene maleic anhydride. A water-dispersible particulate polymeric substance obtained by emulsion polymerization such as acid bar 7 furkyl ester copolymer is suitable, and coating aids include, for example, saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants,
UV absorber, p11 regulator, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener,
A development speed regulator, matting agent, etc. may also be used. The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an anti-halesian layer, a filter layer, etc., as required, to form an internal latent image type silver halide photographic photosensitive material of the present invention. Get the materials. It is useful for the photographic light-sensitive material according to the present invention to be suitable for color use, and in this case, it is preferable to include cyan, magenta and yellow dye image-forming couplers in the silver halide emulsion. You can use whatever you have. In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benz)lyazole, acrylonitrile, and benzophenone compounds in order to prevent dye images from fading due to short-wavelength actinic rays.
It is advantageous to use 0, 326, 327, and 328 (all manufactured by Chippa Iggy) alone or in combination. Examples of the support for the photographic light-sensitive material according to the present invention include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, 2-layer film, baryta paper, polyethylene laminate paper, etc., which have been pretreated 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, shea/ethanolated gelatin, and esterified gelatin. In addition, in the present invention, other hydrophilic binders can be included depending on the purpose, and colloidal albumin, agar, gum arabic, dextran, alginic acid, and acetyl can be hydrolyzed to a content of 19 to 20%. cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cya/acetyl groups such as vinyl alcohol-vinylamino acetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, Hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc. , I N , filter single layer, backing layer, etc. can be added to photographic light-sensitive materials j+n 7A Kl depending on the purpose, and the hydrophilic binder further contains a suitable plasticizer, wetting agent, etc. depending on the purpose. You can force it. Further, the constituent layers of the photographic light-sensitive material according to the present invention can be cured with any suitable hardening agent. Examples of these hardening agents include chromium salts, norconium compounds, aldehyde-based hardeners such as 7-olmaldehyde, halotriazine-based hardeners, polyepoxy compounds, ethyleneleimine-based hardeners, vinyl sulfone-based hardeners, and acryloyl-based hardeners. Further, the photographic light-sensitive material according to the present invention has, on a support, at least one photosensitive emulsion layer containing the internal latent image type silver halide grains according to the present invention, as well as a filter layer, an intermediate layer,
It is possible to provide a large number of various photographic constituent layers such as a protective layer, a subbing layer, a backing layer, and an antihalation layer. When the photographic material of the present invention is used for full color use, at least a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer of each IHL are coated on the support. Ru. In this case, at least one light-sensitive silver halide emulsion layer may contain the internal latent image type silver halide grains according to the present invention, but all the light-sensitive silver halide emulsion layers according to the present invention Internal latent image type halode,
Preferably, it contains silver oxide particles. ! A. Each light-sensitive silver halide emulsion layer may be the same color-sensitive layer or may be separated into two or more layers with different sensitivities. In this case, at least one layer with 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 cuffs, for false colors, for printing, for infrared, for micro,
It can be effectively applied to various uses such as silver dye bleaching, and the colloid transfer method, silver salt diffusion transfer removal 40 jars U.S. Pat. No. 8,087,817, No. 3,185
No. 567 and No. 2,983,606, U.S. Pat. No. 3,253,915 to Weyertz et al., U.S. Pat. No. 3 to Whitemore et al. No. 227,550, U.S. Pat. No. 3,227,5 to Pearl et al.
No. 51, U.S. Pat. No. 3,227,552 to Whitemore et al.
No. 3,415.644 and Rand et al.
, 415,845 and 3,415,646, as well as color diffusion transfer methods.

【Example】

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example-1 Silver bromide core/shell emulsion EM-
1 to EM-2 were created. The core emulsion was a monodispersed silver bromide emulsion, and the emulsion grains had an average grain size of 0.8 μl. This core emulsion was sensitized with gold sulfur.
It was set to 1. The Kano-1 and EH-2 are 51! shown below. It is a silver bromide emulsion prepared using a solution of IIM. (Solution ^-1) Ossein gelatin 11.90° Distilled water 1320j! Polyisopropylene-polyethyleneoxydisuccinate ester sodium salt 10% ethanol aqueous solution
4z14-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene Table 1 Amount listed 28% ammonia water 20.8xlC
OIIE-10,124 mole equivalent Table-1 Tetrazaindene addition amount (solution n-1) Ossein gelatin 3,53゜KBr
150.2y4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene @quantitatively distilled water
549.7w1 Table-2 Particle growth conditions (Solution D-:1) ΔgNO*
213.9g 28% ammonia water 178
．． Adjust to 613.6 mN with 6x1 distilled water. (Solution E-1) 50% KBr aqueous solution I] Necessary amount for Δg adjustment (Solution F-1) 56% acetic acid aqueous solution +3II g 5! JP-A-57-92523 and JP-A-57-92523 at the required amount of 40°C.
7-92524 using the mixing and stirring rock shown in No. 7-92524.
Solution D-1 and solution D-1 were added to solution D-1 using the same "I-temperature mixing method" at the minimum time required to avoid generation of small particles during simultaneous mixing. The addition rate was controlled as shown in Table 2. pAg and pH were controlled by a roller tube pump with variable flow rate while changing the flow rates of Solution E-1, Solution F-1 and Solution It-1. 2 minutes after finishing addition of 0-1, add solution to 1) pA
The obtained core/shell emulsions EH-1 and E were then demineralized and washed with water using a concentrated force, and ossein gelatin 22,7. 4g with distilled water after dispersing in an aqueous solution containing
Amount: 600zZ1. : rR adjusted. The average particle size was 1.8 μl for both EM-1 and EH-2. When the silver halide grains in EM-1 and EH-2 were observed using an electron microscope, it was found that EM-1 was a cubic grain, whereas EH-2 had the (nnl) crystal plane of the present invention. It was found that the particles were After ripening with sodium sulfate and potassium chloroaurate having the following formulas, sensitizing dyes represented by the following formulas were added, respectively. In addition, the magenta coupler 1-(2,4,6-)lichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone was dissolved in diptyl 7-thalerate and ethyl acetate, and a gelatin aqueous solution was prepared. 1 liter of emulsifier dispersed in 11 st. Next, this emulsified dispersion was added to and mixed with each of the above emulsions, a hardening agent was added, and the mixture was coated on a resin-coated paper support so that the coated silver amount was 10.267100 cm<2>, and dried. A part of the sample was heated at 27°C and 60% relative humidity.
It was stored for 1 day (condition-1), 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 sea urchin light through a yellow filter and developed for 3 minutes at 38°C with a developer having the following formulation. 4-Amino-3-methyl-N-ethyl-N-(β-methanesul7onamidoethyl)aniline sulfate 5.02 Sodium sulfite (anhydrous) 2.0 g Sodium carbonate (-hydrate) 15. Oy potassium bromide 1,0. . Add 10 zl of benol alcohol and 11 (align with sodium hydroxide)
However, 20 seconds after the start of development, the entire surface was uniformly exposed to white light of 0°6 Lux for 10 seconds, followed by washing, bleaching, fixing, and washing with water. Dry. Table 3 shows the results of measuring magenta positive images of the obtained samples. Table 3 As can be seen from the results in Table 3, the emulsion of the present invention has a sufficiently high maximum density and also has excellent storage stability of the sample. Example 2 A silver chlorobromide core/shell emulsion E14-3 and VEH-4 having a silver bromide content of 50 mol % and an average grain size of 1.0 μl was prepared as shown below. The core emulsion has a silver bromide content of 5
The 0 mol% average particle diameter was 0.33μ. This core emulsion was sulfur-sensitized and designated as C0RE-2. (Solution ^-3) Ossein gelatin 5 fl., 5 g Distilled water 6900 mN polyisopropylene-polyethyleneoxysuccinic acid ester sodium salt 10% Ethanol aqueous solution 6.5z14-hydroxy-6-methyl-1,3t3at7-tetrazaindene Table -4-described part 1li2
56% water tB liquid 28ml1 old 1.0
1! 1.76
mol C0INE-20,2542 mol < TFI liquid B-3) Ossein gelatin c'4 at 48°
49.9g NaCl1210.4g Polyisopropylene-polyethyleneoxydisuccinate sodium salt 10% diP-nol aqueous solution 4.8m, 14-
Hydroxy-6-methyl-1,3,3a,7-tetrazaindene in the amount listed in Table 4 with distilled water
Set to 2400 apl (mac-3) ΔgNo, 1223g
Distilled water 672ml 1Nil,
011 15.12M Make up to 2400i1 with distilled water. (melting p-a-j KDr
0,688y Macl
116.2g distilled water
2000j+j! (Solution C-3) Vinegar W156% W1 @ 2000a
pl table-4 Each emulsion was tested at 40°C under Japanese Patent Publication No. 85-58288
No. 58-58289, the solution [8-3 and the solution [E
-3 was added by the Gurujet method. The addition rate increased linearly with 113 additions as shown in Table 5. Also, during the addition of each solution, mix using solution F-3 + solution f) pAg It 8.0 (EAg value + 100
z'/)i-: Controlling, mata-melting? Using 1IC-3, the pH of the mixture was controlled to decrease over time as shown in Table 5. Solutions 8-3, E-3, G-3, and F-3 were added using a variable flow rate roller tube pump. Two minutes after the addition of solution E-3 was completed, the pH was adjusted with solution G-3.
was adjusted to 6.0. Table 5: Always wash with regular salt water and use ossein gelatin 8.
Water containing 0g! After dispersing in the liquid, add distilled water to bring the total amount to 500.
Finished with 0 shoulders. As a result of observation using an electron microscope, EH-3 has an average particle size of 1.
The emulsion according to the invention consisted of grains with 0.3 μl (nnl) crystal faces. The contrast emulsion EM-4 was an emulsion consisting of cubic grains with an average grain size of 1.01 .mu.v. EM-5 and EM-6 were created as shown below. Core milk 7i1 is a silver bromide emulsion with an average grain size of 0.30
It was μl. This is C0 as it is without chemical sensitization.
It was designated as nE-3. An emulsion called Kano-5 was prepared in exactly the same manner as EM-3 except that C0RE-3 was used instead of the core emulsion C0RE-2. EH-6 is an emulsion created in exactly the same manner as Kano-4 except that the core emulsion was changed to C0RE-3 instead of C0IIE-2.
shall be. As a result of observation using an electron microscope, EM-5 was an emulsion according to the present invention consisting of grains having an average grain size of 0.95 μl and a (nnl) crystal face. Comparative emulsion EH-6 was an emulsion composed of cubic grains with an average grain size of 0.94 μl. Core/shell emulsions obtained above [8-3 to EH-6
In addition, the magenta coupler 1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone was added to dipyl 7
1 emulsifier dissolved in tallate and ethyl acetate and dispersed in an aqueous gelatin solution! ! did. Next, this emulsion dispersion was added to each of the above emulsions and mixed, and the hardening layer was added to give a coated silver amount of 6.7 art/100 cm.
It was coated on a resin-coated paper support and dried. These samples were wedge exposed through a yellow filter and developed for 3 minutes at 38°C with a developer having the following formulation. 4-7 minnow 3-methyl-N-ethyl-N-(β-methanesul7onamidoethyl) 7niline sulfate 5.0 g Sodium sulfite (anhydrous) 2.0° Sodium carbonate (-hydrate) ts, 4 odor potassium chloride 1.0g benzyl alcohol
Add 10ml water
11 (The pH was adjusted to 1062 with sodium hydroxide) However, after 20 seconds had elapsed after the start of development, the entire surface was uniformly exposed to white light of 0.6 lux for 10 seconds. 6 Then washed with water and bleached. , fixing, washing with water, and drying. Table 6 shows the results of measuring magenta positive images of the obtained samples. Table 6 From the above results, it is clear that the emulsion of the present invention has a sufficiently high maximum density and high sensitivity. Effect of the invention 1 The silver herodenide grains according to the present invention are different from those previously known (
111) Unlike direct bomb emulsions, which consist of grains surrounded by planes and/or (ioo) planes or spherical particles whose planes cannot be identified, good images can be obtained even without any chemical sensitization on the grain surfaces. can be obtained, and if chemical sensitization is performed, higher Dmax can be obtained.
It can be grown. ka compared to the conventional direct emulsion on the pile body.
x%Dmin, has good characteristics in terms of sensitivity and storage stability, and by using the internal latent image type silver halide emulsion unique to the present invention, the maximum density is sufficiently large and the minimum density is sufficiently small. Moreover, a silver halide photographic material with excellent storage stability and high sensitivity can be obtained.

Claims (1)

[Claims] It has 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 directly obtained by surface development while performing a fogging process, the internal latent image type silver halide grains have a crystal plane defined by the Miller index (nn1) (however, n≧2). A direct positive silver halide photographic material comprising: