JPH0547089B2 - - Google Patents

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, 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.

[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 fog nuclei in advance, and uses solarization or the Herschel effect to destroy the fog nuclei or latent image in the exposed area, thereby producing a positive image after development. It is used to obtain images. The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, performs fogging treatment (development nucleation treatment) after image exposure, and then performs surface development, or performs fogging treatment after image exposure. A positive image can be obtained by performing surface development while performing (development nucleation treatment). The fogging treatment (development nucleation treatment) described above may be performed by exposing the entire surface to light, chemically using a fogging agent, or using a strong developer, and further heat treatment. etc. may also 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 halide emulsion, US Pat.
Convergence type, core-shell type, and laminated type are disclosed in US Pat. Furthermore, US Pat. No. 3,761,267 and US Pat. No. 3,206,313 disclose core-shell emulsions which are internally chemically sensitized or doped with polyvalent metals, and JP-A-52-34,213 discloses surface chemical development of dopant-occluding emulsion grains.

[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 required in order to apply these photographic materials to various photographic fields. It is rare. For example, as disclosed in U.S. Pat. Although high sensitivity can be obtained, 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. The stability of the silver emulsion during long-term storage is extremely poor, and the production stability is also poor, which is disadvantageous. On the other hand, as disclosed in Japanese Patent Application Laid-open No. 47-32820,
Silver halide emulsions mainly composed of silver chloride have a relatively high maximum density of positive images obtained, but the minimum density is not sufficiently small, resulting in unclear images. In addition, these emulsions require a long time to prepare unless the grain growth agent is used, and on the other hand, thioether,
The use of a particle growth agent such as substituted thiourea or imidazole has drawbacks such as high minimum concentration and poor storage stability. SUMMARY OF THE INVENTION 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 and a low minimum density, has good storage stability, and can be rapidly processed.

[Means to solve the problem]

In accordance with the object of the present invention, as a result of studies on silver halide crystals, the grain surface has at least one silver halide emulsion layer containing internal latent image type silver halide grains whose surfaces are not fogged in advance,
In a photographic light-sensitive material in which a positive image can be obtained directly by surface development after image exposure, fogging treatment and/or while fogging treatment, the internal latent image type silver halide grains have a mirror index (nn1) ( However, it has been found that the object of the present invention can be solved by a direct positive silver halide photographic material characterized by having a crystal plane defined by n≧2). In the embodiments of the present invention, the silver halide composition is not particularly limited, and silver chloride, silver chlorobromide, silver iodobromide, silver bromide, and silver chloroiodobromide are preferable. A core-shell emulsion is preferred in terms of 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. The particles may have a (100) plane or both a (100) plane and a (111) plane in addition to the crystal plane defined by the Miller index (nn1) (where n≧2). In addition, the particle size is 0.1 to 3 μm, preferably 0.2 to 2.0 μm.
m, more preferably 0.3 to 1.5 μm. Moreover, it is preferable that it is monodisperse. These monodispersed emulsions are preferably mixed or layered as appropriate for use in adjusting gradation. First, silver halide grains having (nn1) planes as used in the present invention will be explained. FIG. 1 is a diagram showing the overall morphology of a silver halide crystal when the outer surface is composed of only (nn1) crystal planes. Moreover, FIG. 2 is a side view seen from the direction of straight lines b ₁ and b ₂ in FIG. 1. There are 24 equivalent crystal planes represented as (nn1) crystal planes. For this reason,
A crystal whose outer surfaces are all (nn1) crystal planes has the form of an icosahedron, and each plane forming the outer surface is an obtuse triangle. There are two types of vertices. In other words, 6 is equivalent to a ₁ in Figure 1.
There are 8 vertices equivalent to vertex and b ₁ . At the vertex a ₁ , 8 planes are in contact with each other, and at the vertex b ₁ , 3 planes are in contact with each other. There are also two types of edges. In other words, there are 24 sides C ₁ equivalent to sides a ₁ b ₁ in Figure 1.
and 12 sides C ₂ which are equivalent to sides a ₁ a ₂ . Next, using the cross-sectional diagram, (nn1) plane, (111) plane,
Explain the relationship between (110) planes. A cross-sectional view of the icosahedron in FIG. 1 along a plane d including the straight line b ₁ b ₂ and perpendicular to the triangle a ₁ a ₂ b ₁ and the triangle a ₁ a ₂ b ₂ is indicated by the solid line 1 in FIG. That is, in FIG. 3, the solid line 1 is the plane d
represents the intersection line between and (nn1) plane. On the other hand, the broken line 2 represents the (110) plane, and the dashed line 3 represents the (111) plane. The directions of the (nn1) plane, (110) plane, and (111) plane are indicated by normal vectors p→, q→, r→. That is, P→=[nn1] (n is a natural number, n≧2), q→
= [110], r→= [111]. θ is the angle formed by two (nn1) crystal planes adjacent to each other with side a ₁ a ₂ as the boundary, and from the restriction that n≧2 and n is a natural number,
110°<θ<180°. In other words, the (nn1) 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.
1/n), thus (nn1)
This is what is displayed. From the above, it is clear that the (nn1) crystal plane according to the present invention is completely different from the conventionally known (111) crystal plane and (110) crystal plane in silver halide microcrystals. Also (100)
There is no need for special explanation that this is different from the crystal plane. On the other hand, Japanese Patent Application No. 59-206765 discloses ``silver iodobromide grains having a crystal plane having a ridge line at the center of the (110) plane.'' In the specification, this crystal plane is named a quasi-(110) plane, and it is stated that ``The angle formed by the two roof-shaped quasi-(110) planes that share a ridgeline is more obtuse than 110°.'' In other words, the quasi-(110) plane refers to the (nn1) 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 in the (nn1) plane. In other words, the (111) plane, (100) plane, or (110) plane may exist. Examples of these are shown in Figures 4 to 11. (111) plane The mixture of 30 and (100) faces forms a 30-hedron (Figs. 5 and 8), a 38-hedron (Figs. 6 and 7), and a 32-hedron (Fig. 4). Dispersibility means particle size r
In contrast, the surface area r ² determines the amount of light received, the amount of sensitization or processing effect that can be received, which has a profound influence on the photographic properties of the emulsion grains, and the volume r ³ that is responsible for the density of the base points of the photographic effect. Synergistic product with particle number n having particle diameter r
Focusing on the fact that nr ³ dominantly determines the characteristics of the photographic emulsion containing the grain, on the other hand, since the grain size r is useful for intuitive understanding, it is a representative that effectively represents the characteristics of the emulsion grain. As a value, the individual particle segment ri
is plotted on the horizontal axis, and the volume r ³ i is plotted on the vertical axis as the frequency ni of the segment.
In a weighted frequency curve in which a weighted frequency nir ³ i is taken as a weight, the mode rm in the weighted frequency curve is simply expressed as follows, following the mode of the statistical value that is generally statistically defined by the maximum frequency of the frequency curve. The standard was dispersibility. In the present invention, monodispersity is defined when 60% or more of the total silver halide grain weight is contained within a grain size ri range with a grain size deviation of ±20% centered on the mode rm 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 is controlled by at least a compound selected from the following general formula (), (), (), or () and a compound having a repeating unit represented by the following general formula (). Most preferred is a method in which the reaction is carried out in the presence of one type of compound. General formula () General formula () General formula () General formula () General formula () In the formula, R ₁ , R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a derivative of an amino group, an alkyl group, a derivative of an alkyl group, an aryl group, Aryl group derivative, cycloalkyl group, cycloalkyl group derivative, mercapto group, mercapto group derivative or -CONH-R ₄ (R ₄ is a hydrogen atom, an alkyl group, an amino group, an alkyl group derivative, an amino group derivative , represents a halogen atom, a cycloalkyl group, a derivative of a cycloalkyl group, an aryl group, or a derivative of an aryl group), and R ₁
and R ₂ may combine to form a ring, R ₅ represents a hydrogen atom or an alkyl group, and X represents the general formula (),
Represents a monovalent group obtained by removing one hydrogen atom from the compound represented by (), () or (), and J is 2
represents a valent linking group. In the general formulas () to (), R ₁ to _{R 4}
Examples of the alkyl group represented by Derivatives of groups include, for example, substituted aromatic residues (two linking groups, e.g. -
NHCO- etc.) alkyl groups (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. methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group, etc.), halogen atom, hydroxy group, carboxy group, mercapto group, alkoxycarbonyl group, or substituted or unsubstituted amino group. alkyl groups (e.g. monochloromethyl group, hydroxymethyl group, 3
-Hydroxybutyl group, carboxylmethyl group,
2-carboxyethyl group, 2-(methoxycarbonyl)ethyl group, aminomethyl group, diethylaminomethyl group, etc.), alkyl groups substituted with cycloalkyl groups (e.g. cyclopentylmethyl group, etc.), general formulas () to ( Examples include an alkyl group substituted with a monovalent group obtained by removing one hydrogen atom from the compound represented by ). Examples of the aryl group represented by R ₁ to _{R 4} include phenyl group, 1-naphthyl group, etc.
Examples of aryl group derivatives include p-tolyl group, m-ethylphenyl group, m-cumenyl group, mesityl group, 2,3-xylyl group, p-chlorophenyl group, o-promophenyl group, p-hydroxyphenyl group, 1-hydroxy-2-naphthyl group,
Examples include m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, o-(methoxycarbonyl)phenyl group, m-(ethoxycarbonyl)phenyl group, 4-carboxy-1-naphthyl group, etc. It will be done. Examples of the cycloalkyl group represented by R ₁ to _{R 4} include a cycloheptyl group, a cyclopentyl group, and a cyclohexyl group, and examples of the derivative of the cycloalkyl group include a methylcyclohexyl group. Examples of halogen atoms represented by R ₁ to _{R 4} include fluorine, chlorine, bromine, and iodine; examples of derivatives of amino groups represented by R ₁ to _{R 4} include butylamino group, diethylamino group, anilino group, etc. Can be mentioned. _R1 ～ _R3
Examples of the mercapto group derivatives represented by include methylthio group, ethylthio group, phenylthio group, and the like. The alkyl group represented by R ₅ preferably has 1 to 6 carbon atoms, and includes, for example, a methyl group and an ethyl group. Especially preferred as R ₅ are a hydrogen atom and a methyl group. J is a divalent linking group, but the total number of carbon atoms is 1 to 20
It is preferable that Among such linking groups, those represented by the following formula (J-) or (J-) are preferred. (J-) (J-) In the formula, Y is -O- or

[Formula] (Here, R ₆ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
represents. Z is an alkylene group (preferably one having up to 10 carbon atoms. An amide bond, ester bond, or ether bond may be present between the alkylene groups. For example, a methylene group, an ethylene group, a propylene group, -CH ₂ OCH ₂ −, −CH ₂ CONHCH ₂ −, −
CH ₂ CH ₂ COOCH ₂ −, −CH ₂ CH ₂ OCOCH ₂ −, −
CH ₂ NHCOCH ₂ - etc.) -O-alkylene group, -
CONH-alkylene group, -COO-alkylene group,
It represents an -OCO-alkylene group or -NHCO-alkylene group (these alkylene groups preferably have up to 10 carbon atoms) or an arylene group (preferably one having 6 to 12 carbon atoms, such as p-phenylene group). Particularly preferable divalent linking groups as J include:
These include: -CONHCH _2- . −CONHCH ₂ CH ₂ −, −
CONHCH ₂ OCOCH ₂ −, −CONHCH ₂ CH ₂ OCOCH ₂ −, −COOCH ₂ −, −
COOCH ₂ CH ₂ −, −COOCH ₂ CH ₂ OCOCH ₂ −,
COOCH ₂ CH ₂ OCOCH ₂ −, The compound having the unit represented by the general formula () may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, methacrylamide, acrylic ester, and methacryl ester. Next, a compound represented by the above general formula (), (), () or () or the above general formula ()
Typical specific examples of compounds having the repeating unit represented by (hereinafter referred to as specific tetrazaindene compounds) are shown below. y: 5 to 50 mol% copolymer y: 5 to 50 mol% copolymer y: 5 to 50 mol% copolymer y: 5 to 50 mol% copolymer Copolymer with y: 5 to 50 mol % The above compound specific tetrazaindene compound according to the present invention is pre-existing in the mother liquor during the formation of the silver halide emulsion, and is added to the copolymer with the production and growth of silver halide grains. It is preferable to increase the amount added.
Therefore, it is preferable to add the specific tetrazaindene compound to the mother liquor of emulsion mixing, a halide ion solution (hereinafter referred to as halide solution), or a silver-containing ion solution. It is a preferable method to prepare a solution and inject it into the emulsion together with a halide solution and/or a silver nitrate-containing ion solution, but in practical terms, adding it to the mixed mother liquor and halide solution simplifies the process and improves productivity. Most preferable for increasing.
By changing the amount of the mixed mother liquor and the specific tetrazaindene supplied during silver halide grain growth, the history of the crystal phase during silver halide crystal growth and the shape (crystal habit) of the final grains can be controlled. 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 silver halide, the temperature during emulsion creation, PH, pAg, etc., but silver halide 1
A range of 10 ^-5 to 2 x 10 ^-1 mol per mole is preferred. In addition, when the specific tetrazaindene compound is a compound having a unit represented by the general formula (), the number of moles of the tetrazaindene moiety:
Addition amount. The method for producing the above-mentioned monodisperse core emulsion is described, for example, in Japanese Patent Publication Nos. 48-36890, 48520-1980, 54-
The double jet method disclosed in No. 65521 and the like can be used. In addition, the 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, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. Such methods are described, for example, in US Pat. No. 1,574,944;
It is described in No. 1623499, No. 2410689, No. 3656955, 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 described in No. 2642361, etc., sensitization can be carried out with a water-soluble gold compound, or with a reduction sensitizer. For such methods, see, for example, US Pat. No. 2,487,850, US Pat.
No. 2983610, etc. can be referred to. Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. For such methods, reference may be made, for example, to US Pat. No. 2,448,060 and British Patent No. 6,18061. 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 particle. Preferred specific examples of metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions are preferably used in a concentration of 1.times.10.sup. ^-8 to 1.times.10.sup. ^-4 mol per mol of silver. The shell of silver halide grains in the present invention is
It is preferable to cover 50% or more of the surface area of the core which has been chemically sensitized or doped with metal ions, and it is particularly preferable to completely cover the core. The above-mentioned double jet method or premix method can be used to form the shell. 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, it can be carried out in the same manner as the chemical sensitization of the core grains. The silver halide grains 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. The monodispersity 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 shell is preferably 20% to 99% based on the total silver halide of the silver halide grains. The composition ratio of the silver halide grains of the present invention is such that the ratio of silver chloride in the grain as a whole is 0% to 100 mol%.
You can choose from a range of It may also contain silver iodide, and its content is preferably 0 to 10 mol%. The silver halide grains of the present invention are preferably emulsions having a structure in which at least two layers having different halogen compositions are laminated. This type of emulsion also consists of an inner core and an outer shell, and can be considered as one type of core/shell structure. Further, the internal latent image type silver halide grains of the present invention may be composed of three or more types of layers. The silver halide composition of the core has a lower chloride content than the silver chloride content of the shell. Preferably it consists primarily of silver bromide and may contain not more than 70% silver chloride, and may contain up to 15% silver iodide. The shape of the particles forming the core may be any shape; for example, it may be cubic, regular octahedral, or a mixture thereof, or may be spherical, tabular, or amorphous. However, the halogen composition of the shell may be different from that of the core, but preferably the silver chloride content of the shell is 10 mol% or more, preferably 20% by mol, more preferably 30 mol% of the silver chloride content of the core. The larger the size, the better. The shell can completely cover the core, or it can selectively cover a portion of the core. The meaning that the particle surface is not fogged in advance means that a test piece coated with the emulsion used in the present invention at a concentration of 35 mgAg/cm ² on a transparent film support was coated with the following surface developer A without exposure. The density obtained when developing for 10 minutes at 20℃ is 0.6, preferably 0.4.
It means not to exceed. Surface developer A Metol 2.5g L-ascorbic acid 10g NaBO _{2.4H 2} O 35g KBr 1g Add water 1 In addition, the silver halide emulsion according to the present invention is prepared by exposing the test piece prepared as described above. , which provides sufficient density when developed with internal developer B having the following formulation. Internal developer B Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (monohydrate) 52.5g KBr 5g KI 0.5g Add water 1 To be more specific, part of the test piece was When exposed to a light intensity scale for a defined time up to 2 seconds and developed in internal developer B for 10 minutes at 20°C, another part of the specimen exposed under the same conditions was exposed to surface developer B. A maximum density of at least 5 times, preferably 10 times, that obtained when developed for 10 minutes at 20°C. The silver halide emulsion according to the present invention can be optically sensitized using a commonly used sensitizing dye. Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative-working silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, reference may be made to Research Disclosure No. 15162 and No. 17643. The photographic material of the present invention can be subjected to image exposure (photography) in a conventional manner and then surface development to easily obtain a positive image directly. 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 a chemical action or an optical action after image exposure. After performing a process that generates fogging nuclei, that is, a fogging process, and/or
Alternatively, surface development may be performed while performing fogging treatment. Here, the fogging treatment can be carried out using a compound that provides full exposure or generates fogging nuclei, that is, a fogging agent. In the present invention, the entire surface exposure is carried out by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface to light. The light source used here may be any light within the sensitivity wavelength range of the photographic light-sensitive material, and high-intensity light such as flash light may be applied for a short period of time, or weak light may be applied for a long period of time. . Further, the total exposure time can be varied over a wide range depending on the photographic material, development processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image. A wide variety of compounds can be used as the fogging agent used in the present invention, and it is sufficient that the fogging agent is present during the development process. (preferably in the silveride emulsion layer), or may be contained in the developer or the processing solution prior to development. The amount used can vary widely depending on the purpose, and the preferred amount is 1 to 1,500 mg per mole of silver halide, preferably 10 to 1,500 mg per mole of silver halide.
~1000mg. When added to a processing solution such as a developer, the preferred amount is 0.01 to 5 g/, particularly preferably 0.05 to 1 g/. Examples of the fogging agent used in the present invention include hydrazines described in U.S. Pat. No. 2,563,785 and U.S. Pat. No. 3719494, same
Heterocyclic quaternary nitrogen salt compounds described in US Pat. No. 3,734,738 and US Pat.
Examples include compounds having adsorption groups on the silver halide surface. Moreover, these fogging agents can also be used in combination. For example, Research Disclosure No. 15162 describes the use of a non-adsorbent 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, both adsorbent and non-adsorbent types can be used, and they can also be used in combination. Specific examples of useful fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-
(4-methylphenyl)hydrazine, 1-acetone-2-phenylhydrazine, 1-acetyl-2
-(4-acetamidophenyl)hydrazine, 1
-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Hydrazine compounds such as 1-methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine; 3-(2-formylethyl)-2-methylbenzothiazolium bromide , 3-(2-formylethyl)-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzoselenazolium bromide, 3-(2
-acetylethyl)-2-benzyl-5-phenyl-benzoxazolium bromide, 2-methyl-3-[3-(phenylhydrazino)propyl]
Benzothiazolium bromide, 2-methyl-3
-[3-(p-tolylhydrazino)propyl]benzothiazolium bromide, 2-methyl-3-
[3-(p-sulfophenylhydrazino)propyl]benzothiazolium bromide, 2-methyl-3-[p-sulfofenylhydrazino)pentyl]benzothiazolium iodide, 1,2- Dihydro-3-methyl-4-phenylpyrido [2,
1-b] Benzothiazolium bromide, 1,2
-dihydro-3-methyl-4-phenylpyrido[2,1-b]-5-phenylbenzoxazolium 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 cycloammonium salt such as benzoselenazolium bromide; 5-[1-ethylnaphtho(1,2-b)thiazolin-2-ylideneethylidene]-1-(2-phenylcarbazoyl ) Methyl-3-(4-sulfamoylphenyl)
-2-thiohydantoin, 5-(3-ethyl-2
-benzothiazolinylidene)-3-[4-(2-formylhydrazino)phenyl]rhodanine, 1
-[4-(2-formylhydrazino)phenyl]
3-phenylthiourea, 1,3-bis[4-(2
-formylhydrazino)phenyl]thiourea and the like. After image exposure, the photographic light-sensitive material having a silver halide emulsion layer according to the present invention forms a positive image directly by exposing the entire surface to light or by surface development treatment in the presence of a fogging agent. 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 for developing the photographic light-sensitive material of the present invention include common silver halide developers, such as polyhydroxybenzenes such as hydroquinone, aminophenols, and 3-pyrazolidones. , ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or mixtures thereof. Specifically, hydroquinone, aminophenol, N
-methylaminophenol, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N,N-diethyl-p-phenylenediamine, diethylamine- o-toluidine,
4-amino-3-methyl-N-ethyl-N-(β
-methanesulfonamidoethyl)aniline, 4
-Amine-3-methyl-N-ethyl-N-(β-
Examples include hydroxyethyl)aniline. 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 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 dihydroxyalkanes,
Furthermore, as a film property improver, for example, a copolymer of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid, a styrene-maleic acid copolymer, a styrene-maleic anhydride half-alkyl ester copolymer, etc. can be used by emulsion polymerization. A water-dispersible fine particulate polymeric substance obtained by this process is suitable, and coating aids include, for example, saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, PH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners,
A development rate regulator, a 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 antihalation layer, a filter layer, etc., as necessary, to form an internal latent image type silver halide photographic light-sensitive material of the present invention. obtain. It is useful to apply the present invention to color photographic light-sensitive materials, and in this case it is preferable 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, benzotriazole, acrylonitrile, and benzophenone compounds to prevent fading of dye images due to short-wavelength actinic rays. 327, same
328 (all manufactured by Ciba Geigy) alone or in combination is advantageous. As the support for the photographic material according to the present invention,
For example, pre-processed polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass,
Examples include baryta paper, polyethylene laminate paper, and the like. 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 binders (binders) can be included depending on the purpose, such as colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl-containing 19
cellulose derivatives such as cellulose acetate hydrolyzed to ~20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl 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,
Contains polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be added to constituent layers of photographic light-sensitive materials such as emulsion layers, intermediate layers, protective layers, filter layers, and backing layers depending on the purpose. The 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 hardeners include chromium salts, zirconiums, aldehydes such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. Can be mentioned. 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, a protective layer, Subbing layer, backing layer,
It is possible to provide a number of different photographic constituent layers, such as antihalation layers. 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, at least one light-sensitive silver halide emulsion layer may contain internal latent image type silver halide grains according to the present invention, but all light-sensitive silver halide emulsion layers contain internal latent image type silver halide grains according to the present invention. Preferably, it contains latent image type silver halide grains. In addition, each light-sensitive silver halide emulsion layer may be the same color-sensitive layer but may be separated into two or more layers having different sensitivities. 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 for general use in black and white,
It can be effectively applied to a variety of applications such as ray, color, false color, printing, infrared, micro, and silver dye bleaching. US patent
3087817, 3185567 and 2983606, U.S. Patent No. 3253915 to Weyertz et al., U.S. Patent No. 3227550 to Whitemore et al., U.S. Patent No. 3227550 to Barr et al.
No. 3227551, U.S. Patent No. 32275552 to Whitemore et al.
No. 3415644 and U.S. Pat. No. 3415645 to Rand et al.
It can be applied to the color image transfer method and the color diffusion transfer method as described in No. 1 and No. 3415646.

【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 emulsions EM-1 to EM-2 were prepared as shown below. The core emulsion is a monodispersed silver bromide emulsion, and the emulsion grains have an average grain size of 0.8 μm.
It was hot. This core emulsion was sensitized with gold sulfur and was designated as CORE-1. EM-1 and EM-2 are silver bromide emulsions prepared using the five types of solutions shown below. (Solution A-1) Ossein gelatin 11.90g Distilled water 1320ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol aqueous solution 4ml 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene Table-1 Amount listed 28% aqueous ammonia 20.8ml CORE-1 0.124 mol equivalent amount

[Table] (Solution B-1) Ossein gelatin 3.53g KBr 150.2g 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene Written amount Distilled water 549.7ml (Solution D-1) AgNO ₃ 213.9g 28% ammonia water 178.6ml Make up to 613.6ml with distilled water. (Solution E-1) 50% KBr aqueous solution Amount required for pAg adjustment (Solution F-1) 56% acetic acid aqueous solution Required amount for PH adjustment At 40°C, JP-A-57-92523 and JP-A-57-
Solution A- using the mixer shown in No. 92524.
Solution D-1 and Solution B-1 were added to Example 1 by a simultaneous mixing method, taking a minimum time during which no small particles were generated. pAg, PH and solution D-1 during simultaneous mixing
The addition rate of was controlled as shown in Table-2. pAg
Control of solution E-1, solution F-1 and solution B is carried out using a roller tube pump with variable flow rate.
-1 while changing the flow rate. 2 minutes after the addition of solution D-1, the pAg was adjusted to 10.4 with solution E-1. After 2 minutes, the pH was adjusted to 10.4 with solution F-1.
Adjusted to 6.0.

[Table] Next, the sample was washed with demineralized water using a conventional method, and after being dispersed in an aqueous solution containing 22.7 g of ossein gelatin, the total volume was adjusted to 600 ml with distilled water. The average particle size was 1.8 μm for both EM-1 and EM-2. When the silver halide grains in EM-1 and EM-2 were observed using an electron microscope, it was found that EM-1 was a cubic grain, whereas EM-2 had the (nn1) crystal plane of the present invention. It was found that the particles were After ripening the core/shell emulsions EM-1 and EM-2 obtained above in sodium sulfate and potassium metal chloride, sensitizing dyes represented by the following formulas were added, respectively. In addition, the magenta coupler 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone was dissolved in dibutyl phthalate and ethyl acetate, and added to an aqueous gelatin solution. A dispersed emulsifier was prepared. Next, this emulsified dispersion was added to and mixed with each of the above emulsions, a hardener was added, and the coated silver amount was 10.2 mg/100 cm ² on a resin-coated paper support.
Dry. A portion of the sample was stored for 3 days at a temperature of 27° C. and a relative humidity of 60% (condition-1), and another portion was stored for 3 days at a temperature of 50° C. and a relative humidity of 80%. (Condition-2). 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-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 5.0g Sodium sulfite (anhydrous) 2.0g Sodium carbonate (monohydrate) 15.0g Potassium bromide 1.0g Benzyl alcohol 10ml Add water and 1 (Adjust the pH 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. Next, it was washed with water, bleached, fixed, washed with water, and dried. Table 3 shows the results of measuring magenta positive images of the obtained samples.

[Table] 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 Silver bromide content 50 mol% as shown below,
Silver chlorobromide core/shell emulsion EM with average grain size of 1.0μm
-3 and EM-4 were created. The core emulsion had a silver bromide content of 50 mol% and an average grain size of 0.33 microns. This core emulsion is sulfur-sensitized.
It was set as CORE-2. (Solution A-3) Ossein gelatin 57.5g Distilled water 6900ml Polyisopropylene-polyethyleneoxy-disuccinate ester sodium salt 10% Ethanol aqueous solution 6.5ml 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene Amount shown in Table 4 56% aqueous acetic acid solution 28ml NH ₄ OH 1.76mol CORE-2 0.2542mol (Solution B-3) Ossein gelatin 48g KBr 449.9g NaCl 210.4g Polyisopropylene-polyethyleneoxydisucci Acid ester sodium salt 10% ethanol aqueous solution 4.8ml 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene Amount shown in Table 4 Make up to 2400 ml with distilled water (Solution E-3) AgNO ₃ 1223 g Distilled water 672 ml NH ₄ OH 15.12 mol Make up to 2400 ml with distilled water. (Solution F-3) KBr 0.688g NaCl 116.2g Distilled water 2000ml (Solution G-3) Acetic acid 56% solution 2000ml

[Table] For each emulsion, at 40℃,
Solution B-3 and solution E-3 were added to solution A-3 by the double-jet method while stirring using the mixer shown in No. 58-58289. The addition rate increased linearly with addition time as shown in Table-5. Also, during each solution addition, solution F-3 was used to adjust the pAg of the mixture to 8.0 (EAg
The pH of the mixed solution was controlled to decrease over time using Solution G-3 as shown in Table 5. Solution B-3, E-3, G-
3. A variable flow rate roller tube pump was used to add F-3. Two minutes after the addition of solution E-3 was completed, the pH was adjusted to 6.0 with solution G-3.

【table】

[Table] Washing with demineralized water was always carried out in a conventional manner, and after dispersing in an aqueous solution containing 80 g of ossein gelatin, the total volume was made up to 5000 ml with distilled water. As a result of observation using an electron microscope, EM-3 was an emulsion according to the present invention consisting of grains having an average grain size of 1.03 μm and a (nn1) crystal face. Also contrasting emulsion EM
-4 was an emulsion consisting of cubic grains with an average grain size of 1.01 μm. EM-5 and EM-6 were created as shown below. The core emulsion was a silver bromide emulsion and had an average grain size of 0.30 μm. This was used as CORE-3 without chemical sensitization. Emulsion EM-5 was prepared in exactly the same manner as EM-3, except that CORE-3 was used instead of CORE-2 as the core emulsion. Emulsion EM-6 was prepared in exactly the same manner as EM-4 except that CORE-3 was used instead of CORE-2 as the core emulsion. 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 μm and a (nn1) crystal face. Also contrasting emulsion EM
-6 was an emulsion composed of cubic grains with an average grain size of 0.94 μm. From the core/shell emulsion EM-3 obtained above
Sensitizing dyes represented by the following formulas were added to EM-6. In addition, the magenta coupler 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone was dissolved in dibutyl phthalate and ethyl acetate, and added to an aqueous gelatin solution. A dispersed emulsifier was prepared. Next, this emulsified dispersion was added to each of the above emulsions and mixed, and coated on a resin-coated paper support so that the coated silver amount was 6.7 mg/100 cm ² by adding hardening.
Dry. 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-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 5.0g Sodium sulfite (anhydrous) 2.0g Sodium carbonate (monohydrate) 15.0g Potassium bromide 1.0g Benzyl alcohol 10ml Add water and 1 (Adjust the pH with sodium hydroxide) (Adjusted to 10.2) However, after 20 seconds have passed after the start of development, for 10 seconds,
The entire surface was uniformly exposed to white light at 0.6 lux.
Next, it was washed with water, marked, fixed, washed with water, and dried. Table 6 shows the results of measuring magenta positive images of the obtained samples.

[Table] 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】

The silver halide grains according to the present invention are different from conventionally known direct positive emulsions consisting of grains surrounded by (111) planes and/or (100) planes, or spherical grains whose planes cannot be specified. , a good image can be obtained without any chemical sensitization on the particle surface, and a higher Dmax can be obtained by chemical sensitization. The aggregate has better characteristics in terms of Dmax, Dmin, sensitivity and storage stability than the conventional direct positive emulsion, and by using the internal latent image type silver halide emulsion unique to the present invention, the maximum density can be sufficiently increased. It is possible to obtain a silver halide photographic light-sensitive material which has a large particle size, a sufficiently small minimum density, and high sensitivity with excellent storage stability.

[Brief explanation of the drawing]

Figures 1 to 8 are schematic diagrams showing the crystal morphology of silver halide grains of the present invention, Figure 9 is an electron micrograph of comparative silver halide grain crystals, and Figures 10 and 11 are diagrams of the present invention. 1 is an electron micrograph of silver halide grain crystals of the invention.

Claims (1)

[Claims] 1 Having at least one silver halide emulsion layer containing internal latent image type silver halide grains whose grain surfaces have not been fogged in advance, and which can be processed after image exposure, after being subjected to fogging treatment, and/or while being subjected to fogging treatment. In a photographic light-sensitive material in which a positive image can be obtained directly by surface development, the internal latent image type silver halide grains have a Miller index (nn1) (however, n≧2).
A direct positive silver halide photographic light-sensitive material characterized by having a crystal plane defined by .