JPH0642041B2 - Direct positive silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a direct positive silver halide photographic light-sensitive material, and more specifically, it is directly exposed to an image and then subjected to a fogging treatment (for example, by exposing the entire surface or performing a surface development treatment in the presence of a fogging agent) to obtain a direct positive image. The present invention relates to a photographic light-sensitive material having an internal latent image type silver halide emulsion layer.

[Prior art]

Conventionally known methods for obtaining a direct positive image are mainly classified into two types. One type is to obtain a positive image after development by using a silver halide emulsion having fog nuclei in advance and destroying the fog nuclei or latent image in the exposed area by utilizing solarization or Herschel effect. It is a thing. The other type uses an internal latent image type silver halide emulsion which has not been fogged in advance, and is fog-processed (development nucleation process) after image exposure.
Then, a positive image can be obtained by performing the surface development, or the surface development while performing the fog treatment (development nucleation treatment) after the image exposure. The above-mentioned fog treatment (development nucleation treatment) may be performed by exposing the entire surface, chemically using a fog agent, or by using a strong developing solution, and further heat treatment. And so on. Of the two methods for forming a positive image, the latter type method generally has higher sensitivity than the former type method and is suitable for applications requiring high sensitivity. Various techniques have been known so far in this technical field. For example, regarding silver halide emulsions of this type, U.S. Pat.Nos. 2,592,250 and 52-34213, 5
8-1412 and 58-1415 disclose conversion type, core-shell type or laminated type, and thioether, imidazole and the like as grain growth agents are disclosed in U.S. Pat.No. 3,574,629 or JP-A-54-100717. It has been described.

[Problems to be Solved by the Invention]

Photosensitive materials capable of forming positive images can be produced by using these known techniques, but further improvement of photographic performance is desired in order to apply these photographic photosensitive materials to various photographic fields. There is. Higher sensitivity is obtained by chemically sensitizing the inside of silver halide grains as disclosed in US Pat. Nos. 3,761,267 and 3,206,313, or by using core / shell type emulsions doped with polyvalent metal ions. However, this type of emulsion has the disadvantage of low image density. 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 emulsion has extremely poor stability for long-term storage and poor production stability. On the other hand, the silver halide emulsion mainly composed of silver chloride disclosed in JP-A-47-32820 has a relatively high maximum density of the obtained positive image, but the minimum density does not become sufficiently small, resulting in unclear images. It becomes an image. Further, these emulsions require a long time for preparation unless the above-mentioned grain growing agent is used. On the other hand, when a grain growing agent such as thioether, substituted thiourea or imidazole is used, the minimum concentration is high and the storage stability is poor. Has the drawback of. Therefore, an object of the present invention is to provide a high-sensitivity internal latent image type silver halide photographic light-sensitive material having a high maximum density and a low minimum density, which has good storage stability.

[Means for solving problems]

 According to the above-mentioned object of the present invention, the constitution of silver halide grains
Based on the results of examination mainly on the conditions, the particle surface is covered in advance.
Containing unexposed internal latent image type silver halide grains
Image exposure with at least one silver halide emulsion layer
After the fogging treatment and / or the fogging treatment
Direct development of positive image by surface development while applying
In the photographic light-sensitive material, the internal latent image type silver halide
At least part of the grain structure is composed of ammine silver complex salt and soluble ha
By novel silver halide precipitation by mixing with a rogenide
After the growth process, the internal latent image type silver halide grains
The structure of the child is represented by the following general formula (I), (II) (III), or (I
A compound represented by V) and a compound represented by the following general formula (V)
At least one selected from compounds having repeating units
Halo, characterized in that it is carried out in the presence of certain compounds
We have found a solution to silver photographic material. General formula (I)General formula (II)General formula (III)General formula (IV)General formula (V)Where R₁, R₂And R₃Can be the same or different
Hydrogen atom, halogen atom, hydroxyl
Groups, amino groups, derivatives of amino groups, alkyl groups, alkyl groups
Group derivative, aryl group, aryl group derivative, cyclo
Low alkyl group, cycloalkyl group derivative, mercapto
Group, mercapto group derivative or -CONH-R_Four(R_FourIs hydrogen
Atoms, alkyl groups, amino groups, derivatives of alkyl groups,
Derivatives of mino groups, halogen atoms, cycloalkyl groups,
A derivative of a chloroalkyl group, an aryl group or an aryl group
Represents a derivative. ), And R₁And R₂Combine to form a ring
May be formed, R_FiveRepresents a hydrogen atom or an alkyl group
X is the general formula (I), (II), (III) or (IV)
Monovalent group J obtained by removing one hydrogen atom from the represented compound.
Represents a divalent linking group. In the above embodiment of the present invention, an ammine complex salt and a soluble halogen
Precipitate formation with a solvent is pH ≦ 10, preferably pH 9.5-6.0
While neutralizing to the range of pAg 6-9.
And are preferred. What kind of silver halide composition should be used?
It may be. For example, silver bromide, silver chlorobromide, silver iodobromide, salt
Examples thereof include silver iodide, silver chloride and silver chlorobromoiodide. halogen
In the silver halide composition, silver chloride is 0 to 100 mol%, preferably
0-75 mol%, more preferably 0-50 mol%
The silver halide content is preferably 0 to 10 mol%. Emulsion grains consist of inner core and at least one outer shell.
Core-shell type or laminated type particles consisting of
Further preferably, the inner core contains at least 50 mol% of silver bromide.
It is preferable to have. Further, the emulsion grain size is 0.1 to 2.0 μm, preferably 0.2 to 1.5 μm.
m and monodisperse particle size distribution is preferred. In the core-shell type particles, polyvalent metal ions are added to the inner core.
It is preferable that they have been doped and chemically sensitized by
The ratio of the outer shell to the total particles is 20 to 99 mol%
It is preferable. On the other hand, a crystal singularity is formed at the lamination interface.
In the case of laminated grains, the silver halide composition of the inner and outer shells
To give a difference of 30 mol% or more in the content of silver chloride.
Preferably. The ammine silver complex salt used in the present invention is a complex salt in an aqueous solution of silver nitrate.
Add more than equivalent amount of ammonia to produce silver-ammonia complex
The feature of the present invention is that it contains silver ions.
Solution containing halogen chloride by mixing liquid and halide solution
At least a portion of the silver halide raw material in the production of silver halide
Ammoniacal silver nitrate that produced the ammine silver complex salt
The use of a solution and the formulas (I) to (V)
The compound to be present in the composition of the silver halide grains
It is in. Further, the so-called monodispersibility in the present invention means that the particle diameter r is
Therefore, the amount of light received and the ripeness that have a profound effect on the photographic characteristics of emulsion grains
Surface area r that determines the amount of acceptance of treatment or treatment effect²And photo effect
Volume r related to the existing density of fruit base points³Is the particle diameter r
Synergistic product nr with the number of particles n³By including the particle
Focusing on dominantly determining the characteristics of true emulsions,
Since the diameter r is useful for intuitive grasp,
As a representative value that effectively represents the characteristics,
The horizontal axis is the horizontal axis and the vertical axis is the volume r³i is weighted to the frequency ni of the segment
Weighted frequency nir³Weighted frequency song with i
A line is generally defined statistically by the maximum frequency of the frequency curve.
The weighted frequency curve according to the mode that is the systematic value
The mode rm in the above is taken as the standard of monodispersity. In the present invention, the particle size is centered around the mode rm defined above.
Weight of all silver halide grains within the range of grain size ri with a deviation of ± 20%
When it contains 60% or more of particles, it is considered to be monodisperse. This
In the clear, the monodispersity is 70% or more, preferably 80% or more.
It Next, the present invention will be described in detail. In the general formulas (I) to (V), R₁~ R_FourRepresented by
Examples of the alkyl group include a methyl group, an ethyl group,
Propyl group, benzyl group, hexyl group, octyl group, a
Sopropyl group, sec-butyl group, t-butyl group, 2-carb
Examples of the derivative of an alkyl group include a lubonyl group.
Is, for example, substituted with an aromatic residue (a divalent linking group, eg
For example, —NHCO— or the like) alkyl group (for example,
Benzyl group, phenethyl group, benzhydryl group, 1-naphth
Cylmethyl group, 3-phenylbutyl group, benzoylami
Noethyl group, etc.), alkyl group substituted with an alkoxy group
(For example, methoxymethyl group, 2-methoxyethyl group, 3
-Ethoxypropyl group, 4-methoxybutyl group, etc.),
Rogen atom, hydroxy group, carboxy group, mercapto
Groups, alkoxycarbonyl groups or substituted or unsubstituted
Alkyl groups substituted with amino groups of
Methyl group, hydroxymethyl group, 3-hydroxybutyl
Group, carboxytyl group, 2-carboxyethyl group, 2
-(Methoxycarbonyl) ethyl group, aminomethyl group,
Diethylaminomethyl group, etc.), cycloalkyl group
A substituted alkyl group (eg cyclopentylmethyl group
Etc.), a compound represented by the above general formula (I) to (IV)
Alkyl substituted with a monovalent group except for one hydrogen atom
Groups and the like. R₁~ R_FourExamples of the aryl group represented by
Examples thereof include a nyl group and a 1-naphthyl group.
Examples of the conductor include p-tolyl group and m-ethylpheny
Group, m-cumenyl group, mesityl group, 2,3-xylyl group
Group, p-chlorophenyl group, o-promophenyl group, p
-Hydroxyphenyl group, 1-hydroxy-2-naphthyl
Group, m-methoxyphenyl group, p-ethoxyphenyl group
Group, p-carboxyphenyl group, o- (methoxycarbo group
Nyl) phenyl group, m- (ethoxycarbonyl) phenyl
Group, 4-carboxy-1-naphthyl group and the like.
It R₁~ R_FourAs the cycloalkyl group represented by, for example,
For example, cycloheptyl group, cyclopentyl group, cyclohexyl
Group, etc., as a cycloalkyl group derivative
Is, for example, a methylcyclohexyl group. R
₁~ R_FourExamples of the halogen atom represented by
R, chlorine, bromine, iodine, etc.₁~ R_FourAmino represented by
Examples of the derivative of the group include butylamino group and diethyl
Examples thereof include an amino group and an anilino group. R₁~ R₃Represented by
Examples of the mercapto group derivative to be used include
O group, ethylthio group, phenylthio group and the like. R_FiveThe alkyl group represented by preferably has 1 to 1 carbon atoms.
6 and examples thereof include a methyl group and an ethyl group. R_FiveOf these, a hydrogen atom and a methyl group are particularly preferable. J is a divalent linking group, but has a total carbon number of 1-20.
And are preferred. Among such linking groups, the following formula (J-
Those represented by I) or (J-II) are preferable. (JI)(J-II)In the formula, Y is -O- or(Here R₆Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Group). Z is an alkylene group (preferably having up to 10 carbon atoms.
An amide bond, an ester bond, or
Alternatively, an ether bond may be interposed. For example
Group, ethylene group, propylene group, -CH₂OCH₂−, −CH₂
CONHCH₂−, −CH₂CH₂COOCH₂−, −CH₂CH₂OCOCH₂-, CH₂
NHCOCH₂-Etc.) -O-alkylene group, -CONH-alkyle
Group, -COO-alkylene group, -OCO-alkylene group
Or -NHCO-alkylene group (these alkylene groups are
More preferably, it has up to 10 carbon atoms) or an arylene group (preferably
More preferably, it has 6 to 12 carbon atoms. For example, p-phenylene group
Etc.) Particularly preferred divalent linking groups as J are as follows.
Is mentioned. −CONHCH₂−, −CONHCH₂CH₂−, −CONHCH₂OCOCH₂-,-
CONHCH₂CH₂CH₂OCOCH₂−, −COOCH₂−, −COOCH₂CH₂-,
−COOCH₂CH₂OCOCH₂−, −COOCH₂CH₂CH₂OCOCH₂-,The compound having a unit represented by the general formula (V) is
It may be a polymer or a copolymer,
Examples of the limer include acrylamide and methacryl
Examples include amides, acrylic esters, and methacrylic esters.
You can Next, the general formula (I), (II), (III) or (I
V) or a compound represented by the general formula (V)
A compound having a repeating unit (hereinafter, referred to as
Tetrazaindene compounds that can be used)
Here is an example: (1)(2)(3)(4)(5)(6)(7)(8)(9)(Ten) (11)(12)(13) (14) (15)(16)(17)(18)(19)(20)(twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26)(27)(28)(29)(30)(31)(32)y: 5 to 50 mol% copolymer (33)y: Copolymer of 5 to 50 mol% (34)y: Copolymer of 5 to 50 mol% (35)y: Copolymer of 5 to 50 mol% (36)y: Copolymer of 5 to 50 mol% The above compound according to the present invention (hereinafter simply referred to as tetrazaindene
Compound) is added to the mother liquor when the silver halide emulsion is formed.
The presence of silver halide grains and
Therefore, it is preferable to increase the addition amount. Therefore, the present invention
The tetrazaindene compound of
Genide ion solution (hereinafter referred to as halide solution) or
Is preferably added to the ammoniacal silver nitrate solution
In addition, separately prepare the tetrazaindene compound solution of the present invention.
With a halide solution and / or an ammoniacal silver nitrate solution
Injecting both into the emulsion is a preferable method, but
The process is to add it to the mixed mother liquor and halide solution.
Is most preferable in order to simplify the process and increase the productivity. Mixed mother liquor
And tetrazaindene supplied during silver halide grain growth
By changing the amount of
Control habit history and shape of final product particles (crystal habit)
can do. The amount of tetrazaindene compound added depends on the halo to be obtained.
Grain size of silver gentide grains, composition of silver halide, during emulsion preparation
Depending on the manufacturing conditions such as temperature, pH, pAg, etc.,
10 per mol of silver halide formed^-Five~ 2 x 10^-1Mole
Ranges are preferred. In the method of the present invention, the tetrazaindene as described above is used.
Halide solution and ammoniacal silver nitrate in the presence of phosphorus compounds
Mix the solutions to form a silver halide emulsion.
What is ammoniacal silver nitrate solution?
A silver-ammine complex solution was prepared by adding more than the equivalent amount of nia.
However, when ammoniacal silver nitrate is used, the solution does not mix.
At the moment when it was added to the mixture, the silver-ammine complex was compressed.
The concentration of free silver ions is extremely high, and the silver nitrate solution is added directly.
It is much smaller than the case of addition, and the formation of silver oxide is extremely small.
Since it disappears, it is rarely reduced to metallic silver.
Strongly combined with the effect of the tetrazaindene compound
The effect of suppressing the generation of fog is obtained. On the other hand, when using an ammoniacal silver nitrate solution, silver ion dissolution
A large amount of ammonia is contained in the liquid mixture of the liquid and the halide solution.
The pH of the liquid increases because it is brought in, but milk containing silver chloride
Agents turnip if the form is carried out at too high a pH.
The ammoniacal silver nitrate solution may increase
And a halide ion solution at the time of mixing
Keep pH preferably below 10, more preferably 6-9.5
It is desirable to do. To keep the pH in the above condition, ammoniacal silver nitrate
Solution that is the mother liquor of the mixture of the solution and the halide ion solution
A colloidal solution and / or halide ion solution
Method, add an appropriate amount of acid, or mix the acid solution.
Add to the mixture continuously or intermittently as the
It is possible to take such a method. Acid used to adjust pH
Examples include inorganic acids such as sulfuric acid and nitric acid, acetic acid, and
It is possible to use various acidic substances such as organic acids such as enoic acid.
You can In the method of the present invention, as described above, silver halide grains are used.
Depending on the amount of tetrazaindene compound depending on the child formation
The crystal habit and shape of the obtained silver halide grains change.
However, the crystal habit, grain size distribution and shape of silver halide microcrystals
The Journal of Photographic Science
Su (Jornal of Photographic Scisnce) Volume 12 245-251
Page (1964), Vol. 27, pages 47-53 (1979) and many other sentences
As stated in the dedication, silver ions in the liquid during crystal formation
It depends on the concentration, ie pAg. In the emulsion according to the present invention, an ammoniacal silver nitrate solution
Of grain formation process including mixing of cation and halide ion solution
To maintain the pAg of the mixture within the range of 4-9.
preferable. pAg is the grain of the silver halide emulsion to be obtained
Depending on the crystal habit, shape, particle size distribution, etc. of
It may be maintained at a constant value within the above range, and is also disclosed in JP-A-59-466
In the process of adding silver ion solution as described in No. 40
You may change it. As a control method of pAg, pAg control
Mixing of water-soluble bromide ion and water-soluble chloride ion as liquid
A method using a combined solution is preferable. That is, when mixing
Add the amount of rogenide ion added per unit time to that of silver ion
Almost equal to the added amount, and at the same time, the water-soluble bromide ion
A pAg control solution consisting of a mixture of chloride and chloride ions
Controlling pAg value by adding at the ratio shown by
It is preferable in terms of the properties, the monodispersibility of the obtained particles, and the halogen composition.
Good Formula Y = KX [where X is the Cl / Br ratio (mol
Ratio) and K are positive numbers from 40 to 1200. ] Further, the value of K is an emulsion mother liquor for forming and suspending silver halide.
Depending on the temperature of
And are preferred. K = (634.9-12.75t + 0.07938t²) S where t is an emulsion mother liquor that produces and suspends silver halide
(° C) and S are positive numbers of 3 to 1/3. The silver ion solution (first
The amount of halide ions is approximately the same as the amount of silver ions in the liquid).
The halide ion solution (second liquid) should be
Although the pAg control solution is added, the change in pAg at this time is sufficient.
Adjust the concentration and / or addition rate so that
It is prepared and added. The addition rate of the pAg control solution depends on the addition rate of the second solution.
When it is close to the acceleration, the concentration of the pAg control liquid is the total of the second liquid.
1/10 or less of halide ion concentration is preferable.
The addition rate can be set to 1/10 or less of the addition rate of the second liquid
In some cases, it may be equal to the halide ion concentration of the second liquid.
Yes. The flow rate control technique that is usually used is used to control the addition rate.
Available. The preferred temperature during the production of silver halide in the present invention is 20
It is -80 ° C, more preferably 30-70 ° C. Suitable as an internal latent image type silver halide emulsion grain according to the present invention.
Commonly used core-shell type particles and laminated type particles are
As far as the child structure cross section is concerned,
Both are made up of one layer of outer shell and are considered equivalent, but the core-shell type
, Its inner core has already matured as photosensitive particles.
On the other hand, in the laminated type, the inner core is covered with an outer shell.
Creates a photonucleus at its interface due to crystal strain, etc.
It is roughly distinguished as what it does. But Naga
Even in the core-shell type, the core (inner core) and shell (outer core)
Layered by adjusting the silver halide composition of the shell)
Factor is introduced, and is given from the outer shell surface toward the inside.
Can spread chemical aging effect or bleaching effect
Therefore, in the present invention, the two may be distinguished as long as there is no discrepancy.
It is expressed as a [core / shell] type. Further, the shell of the [core / shell] type particles according to the present invention has 2
It may be a multilayer shell having more than one layer. The shell of the silver halide grain of the present invention is a silver halide
A or the inner shell surface may be completely covered,
Alternatively, a part of the surface may be selectively coated. In the present invention, the outermost shell layer covers 10% or more of the particle surface.
It is preferable to cover it. In the case of a multilayer shell in the present invention, it is adjacent to the outermost layer
The layer contains less silver chloride than the outermost layer, but this difference is the outermost
At least 10 mol% or less based on the silver chloride composition ratio of the layer
It is preferable to have a very low silver chloride composition ratio. However
In the laminated type, the difference in the silver chloride composition between the core and the shell average is
30 mol% or more is preferable. Meet these conditions
Any silver halide composition may be used. For example
Silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide
Can be mentioned. The multilayer shell is at least the outermost layer and the layer adjacent to it.
Layers consisting of different silver halide compositions
May have a structure in which
Is the radial direction of the silver halide grains and is continuous silver halide
It may have a structure in which the composition changes. The multilayer shell in the silver halide grain of the present invention has two layers.
It may be a multi-layer shell composed of more layers. Core of the [core / shell] type silver halide grain of the present invention
Contains at least 50 mol% of silver bromide.
And further contains silver chloride and / or silver iodobromide
You can leave. Shape of silver halide grains forming the core
May have any shape, for example, cubic crystal, regular octahedron
It may be a body, or a mixture of these,
It may be spherical, tabular or amorphous particles. The core of the present invention
Obtain the average grain size and grain size distribution of the constituent silver halide grains.
Can be changed widely depending on the photographic performance
However, it is more preferable that the particle size distribution has a narrow distribution. That is, the book
The silver halide grains that make up the core of the invention are substantially
It is preferably dispersible. For example, the particle size can be increased from 10,000 times to 50,000 times with an electron microscope.
When enlarging and projecting, the particle diameter or when projected on the print
It can be obtained by measuring the area of
It is assumed that there are 1000 or more children indiscriminately. ). The method for producing the monodisperse core emulsion is described in, for example, JP-B-48.
-36890, JP-A-54-48520, JP-A-54-65521, etc.
The double jet method can be used. Other than this
The premix method described in Japanese Patent Publication No.
sell. When a monodisperse emulsion is produced by the method of the present invention,
Fine halogen separately prepared in mother liquor containing colloid
Silver halide crystals (so-called seed emulsion) were added in advance, and then
Ammoniacal silver nitrate solution in the presence of ruzaindene compounds
And a halide ion solution to add the seed emulsion grains.
It is preferable to grow to the required grain size. For this occasion
The conditions for preparing the seed emulsion are limited
There is no place. The core of the silver halide grain in the present invention is chemically sensitized.
Or metal ions may be doped.
Many methods are known for chemical sensitization. That is,
Sulfur sensitization, gold sensitization, reduction sensitization, precious metal sensitization and
This is a sensitization method that is a combination of sensitization methods. As a sulfur sensitizer
Is thiosulfate, thioureas, thiazoles, rhodani
And other compounds can be used. like this
Such methods include, for example, U.S. Patents 1,574,944 and 1,623,499,
No. 2,410,689, No. 3,656,955, etc. The core of the silver halide grain used in the present invention is, for example,
U.S. Patents 2,399,083, 2,597,856, 2,642,361
Sensitization with a water-soluble gold compound, as described in
Can also be sensitized with a reduction sensitizer
It For such a method, for example, U.S. Pat.
See 850, 2,518,698, 2,983,610, etc.
can do. Furthermore, for example, platinum, iridium, palladium, etc.
It is also possible to sensitize precious metals using the precious metal compounds of
It For such a method, for example, U.S. Pat.
No. 060 and British Patent 618,061 may be referred to.
Wear. The core of the silver halide grain in the present invention is metal-doped.
can do. To dope the core with metal ions
Is, for example, in any process that forms core particles.
Can be added as a water-soluble salt of metal ions
It Iridium as a preferred specific example of the metal ion,
Lead, antimony, bismuth, gold, osmium, rhodium
There are metal ions such as. These metal ions are preferred
Is 1 × 10 for 1 mol of silver^-8~ 1 x 10^-FourUsed in molarity
Used. The shell of the silver halide grain in the present invention is chemically
Either sensitized or doped with metal ions
Cover 50% or more of the core surface area
Is more preferable, and the core is completely covered.
Is particularly preferable. The method for forming the shell is the double jet method or pre-press method described above.
A mixed method can be used. In addition, the core emulsion contains fine particles of halo.
Formed by Ostwald ripening mixed with silver genide
You can also The silver halide grains of the [core / shell] type emulsion of the present invention are
The grain surface is not chemically sensitized or sensitized
Even if it is present, it is preferably in a slight degree. When the surface of the silver halide grain of the present invention is chemically sensitized,
It can be carried out in the same manner as the chemical sensitization of the core particles.
It The silver halide grains in the present invention are formed after the shell is formed.
However, it is preferable that the particle distribution is narrow and that the particles are substantially monodisperse.
Good That is, the silver halide grains as a whole are substantially
It is preferably monodisperse. Here, the monodisperse silver halide grains as a whole are
Mode particle size rm is centered within ± 20% particle size range
The silver rogenide weight is 60% or more of the total weight of silver halide.
It is preferably 70% or more, particularly preferably 80
Percentage is more than%. The ratio of the silver halide of the core and the shell of the present invention is optional.
Although it can be determined, the ratio of shells depends on the total silver halide grains.
20% to 99% based on silver halide is preferred
Yes. In the composition ratio of the silver halide grain of the present invention, the whole grain
As for the ratio of silver chloride, 0 to 75 mol% is preferable. The fact that the particle surface is not pre-blended means that
35 mg Ag on a transparent film support used for light
/ dm²The test piece coated so that
The density obtained when developed with Developer A at 20 ° C for 10 minutes is
0.6 It means not exceeding 0.4, preferably 0.4. Surface developer A Metol 2.5g l-Ascorbic acid 10g NaBO₂・ 4H₂O 35 g KBr 1 g Water was added 1 In addition, the silver halide emulsion according to the present invention was as described above.
After exposing the test piece prepared by
It gives a sufficient density when developed by. Internal developer B Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water added 1 g Second
Exposure to the light intensity scale over a defined time
When exposed to light and developed with internal developer B at 20 ° C for 10 minutes,
Another part of the test piece exposed under one condition was treated with the surface developer A.
Less than what you would get if developed at 20 ° C for 10 minutes
Both show maximal concentrations of 5-fold, preferably at least 10-fold
It is a thing. The silver halide emulsion according to the present invention is a commonly used sensitizing color.
It can be optically sensitized by the element. Internal latent image type
Super color enhancement of silver halide emulsions, negative type silver halide emulsions, etc.
The combination of sensitizing dyes used for sensitization is the halogenated compound of the present invention.
It is also useful for silver emulsions. Lisa for sensitizing dyes
Reach Disclosure No.151
No. 62 and No. 17643 can be referred to. The photographic light-sensitive material of the present invention is image-exposed (photographed) by an ordinary method.
After that, the surface can be easily developed to make a positive image.
You can get a statue. That is, create a positive image directly
The major steps are the internal, non-pre-laden inner latent of the present invention.
A photographic light-sensitive material having an image-type silver halide emulsion layer is formed into an image.
Fog nuclei by chemical or optical action after exposure
And / or after the fogging treatment is performed.
Or because surface development is performed while performing fogging treatment
Become. Here, the fogging process gives a full exposure or
Compounds that produce fog nuclei, i.e.
I can. In the present invention, the entire surface exposure refers to a photosensitive material which is imagewise exposed.
Immersion or wetting in image or other aqueous solutions
Then, uniform exposure is performed over the entire surface.
The light source used here is the photosensitive wavelength range of the photographic light-sensitive material.
Any light inside can be used, like flash light
You can illuminate with high intensity light for a short time
You can apply it for a long time. Also, the time for full exposure is photographic material
Depending on the material, processing conditions, type of light source used, etc., the final
A wide range to obtain the best positive image
You can A wide variety of fog agents used in the present invention
The compound can be used.
It may be present at any time, for example, a support of a photographic light-sensitive material or more.
In the outer constituent layers (especially in the silver halide emulsion layer)
Preferred), or prior to the developer or development process
It may be contained in the treatment liquid. Also, the amount used
It can be changed over a wide range according to
Is a halogen when added to the silver halide emulsion layer.
1-1500 mg, preferably 10-1000 mg per mol of silver halide
It Further, it is preferable when it is added to a processing solution such as a developing solution.
The addition amount is 0.01 to 5 g /, particularly preferably 0.05 to 1 g /
It Examples of the fogging agent used in the present invention include US Pat.
Hydrazine described in 3,785 and 2,588,982
Or hydra described in US Pat. No. 3,227,552
Zido or hydrazone compounds; US Pat. No. 3,615,615,
3,718,479, 3,719,494, 3,734,738, 3,7
Heterocyclic quaternary nitrogen salt compounds described in 59,901;
Acylhydrazinophenyl described in US Pat. No. 4,030,925
Has an adsorbing group on the surface of silver halide such as thioureas
Compounds. Also, these fogging agents are
It can also be used. For example, Research Disclosure
(Reseach Disclosure) No. 15162 No adsorption
Type fogging agent used in combination with adsorption type fogging agent
This combined technique is also effective in the present invention.
It The fogging agent used in the present invention may be an adsorption type or a non-adsorption type.
Either can be used, or they can be used together.
I can do it. Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydra
Zin hydrochloride, 1-formyl-2- (4-methylphenyi)
Le) hydrazine, 1-acetyl-2-phenylhydrazide
1-acetyl-2- (4-acetamidophenyl)
Hydrazine, 1-methylsulfonyl-2-phenylhi
Drazine, 1-benzoyl-2-phenylhydrazine,
1-methylsulfonyl-2- (3-phenylsulfone
Namidophenyl) hydrazine, formaldehyde
Hydrazine compounds such as phenylhydrazine; 3- (2-pho
Rumilethyl) -2-methylbenzothiazolium bromide
Id, 3- (2-formylethyl) -2-propylben
Zothiazolium bromide, 3- (2-acetylethyi)
) -2-benzylbenzoselenazolium bromide,
3- (2-acetylethyl) -2-benzyl-5-phen
Nyl-benzoxazolium bromide, 2-methyl-
3- [3-phenylhydrazino) propyl] benzothia
Zolium bromide, 2-methyl-3- [3- (p-to
Rylhydrazino) propyl] benzothiazolium bromide
Id, 2-methyl-3- [3- (p-sulfaphenyl
Hydrazino) propyl] benzothiazolium bromide
2-methyl-3- [p-sulfophenylhydrazide
No) Pentyl] benzothiazolium iodode, 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 [2,2
1-b] N-substitution such as benzoselenazolium bromide
Quaternary cycloammonium salt; 5- [1-ethylnaphtho
(1,2, b) thiazoline-2-ylidene ethylidene]
-1- (2-phenylcarbazoyl) methyl-3- (4
-Sulfamoylphenyl) -2-thiohydantoin,
5- (3-Ethyl-2-benzothiazolinylidene) 3-
[4- (2-formylhydrazino) phenyl] loader
Nin, 1- [4- (2-formylhydrazino) pheny
] -Phenylthiourea, 1,3-bis [4- (2-
Formylhydrazino) phenyl] thiourine, etc.
It Photographic material having a silver halide emulsion layer according to the present invention
After image exposure, full exposure or in the presence of fog
To form a positive image directly by surface development
It This surface development method is essentially a method of using a silver halide solvent.
It means to be processed with a developing solution that does not contain it. For the surface developer used for developing the photographic light-sensitive material according to the present invention
As a developer that can be used in the
Silver halide developer, such as polyquine such as hydroquinone
Droxybenzenes, aminophenols, 3-virazo
Redones, ascorbic acid and its derivatives, reductone
, Phenylenediamines, etc. or mixtures thereof
Be done. Specifically, hydroquinone, aminophenol,
N-methylaminophenol, 1-phenyl-3-pyra
Zolidone, 1-phenyl-4,4-dimethyl-3-pyra
Zolidone, 1-phenyl-4-methyl-4-hydroxy
Methyl-3-pyrazolidone, ascorbic acid, N, N-
Diethyl-p-phenylenediamine, diethylamine
-O-toluidine, 4-amino-3-methyl-N-ethyl
Ru-N- (β-methanesulfonamidoethyl) anili
4-amine-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline and the like. these
The developer is included in the emulsion in advance and immersed in a high pH aqueous solution.
It is also possible to act on silver halide. The developer used in the present invention has a specific fog.
May contain an inhibitor and a development inhibitor, or
Any of these developer additives may be added to the constituent layers of the photographic light-sensitive material.
It is also possible to incorporate into. The silver halide emulsion according to the present invention may be wet depending on the purpose.
Agents, film property modifiers, coating aids, and other photographic additives.
You can also get it. Wetting agents include, for example, dihydroxy
Sialkane and the like, and further as a film property improving agent
Is, for example, alkyl acrylate or alkyl meta.
Copolymerization of acrylate with acrylic acid or methacrylic acid
Combined, styrene-maleic acid copolymer, styrene anhydride
Emulsion polymerization of oleic acid halfalky ester copolymer
A water-dispersible fine particle polymer substance obtained by
Examples of coating aids include saponin and polyene.
It includes ethylene glycol lauryl ether and the like. That
Other photographic additives, gelatin plasticizer, surface active
Agent, ultraviolet absorber, pH adjuster, antioxidant, antistatic
Agents, thickeners, graininess improvers, dyes, moldants, whitening
Agents, development speed regulators, matting agents, etc. can also be used.
It The silver halide emulsion prepared as described above may be used if necessary.
Through the undercoat layer, antihalation layer, filter layer, etc.
The internal latent image type silver halide copy of the present invention coated on a support.
A true photosensitive material is obtained. There is no application to color photographic light-sensitive materials according to the present invention.
For this purpose, in this case, in the silver halide emulsion, cyan,
Black and yellow dye image-forming couplers
Is preferred. What is usually used as a coupler
Can be used. It also prevents fading of dye images due to short wavelength actinic rays.
UV absorbers, for example thiazolidone, benzotri
Azole, acrylonitrile, benzophenone compounds
It is useful to use
326, 327 and 328 (all manufactured by Ciba Geigy)
Single use or combined use is advantageous. The support of the photographic light-sensitive material according to the present invention is, for example, an essential component.
Polyethylene terephthalate powder prepared as needed
Rum, polycarbonate film, polystyrene fill
Film, polypropylene film, cellulose acetate film
Film, glass, baryta paper, polyethylene laminate
Examples include paper. The silver halide emulsion layer according to the present invention contains a protective colloid.
As a binder, in addition to gelatin,
You can use a suitable gelatin derivative according to your needs.
It Examples of suitable gelatin derivatives include acyl
Gelatin, guanidylated gelatin, carbamylated gelatin
Chin, cyanoethanolated gelatin, esterified gelatin
And the like. Further, in the present invention, other hydrophilic bonds may be used depending on the purpose.
An agent (binder) can be included, and a colloidal agent
Lubmin, agar, gum arabic, dextran, algi
Cell hydrolyzed to 19-20% containing acid and acetyl
Cellulose derivatives such as rose acetate, polyacryloyl
Lamide, imidized polyacrylamide, casein, bi
Of nyl alcohol-vinyl amino acetate copolymer
Such as urethane carboxylic acid group or cyanoacetyl group
Including vinyl alcohol polymer, polyvinyl alcohol
, Polyvinylpyrrolidone, hydrolyzed polyvinyl acetate
With vinyl, a protein or saturated acylated protein.
Polymer obtained by polymerization with the monomer
Viridine, polyvinylamine, polyaminoethylmethac
Contains emulsions such as relate and polyethyleneamine.
Photographs of intermediate layer, protective layer, filter layer, backing layer, etc.
It can be added to the optical material constituent layer according to the purpose.
In addition, the above-mentioned hydrophilic binder has an appropriate plasticity according to the purpose.
Agents, wetting agents and the like can be included. Further, the constituent layers of the photographic light-sensitive material according to the present invention can be any suitable
It can be hardened with various hardeners. These hard
As film agents, chromium salts, zirconiums, formua
Aldehydes such as aldehydes and mucohalogen acids, halo
Riazine type, polyepoxy compound, ethyleneimine type,
Examples include vinyl sulfone-based and acryloyl-based hardeners.
Be done. Further, the photographic light-sensitive material according to the present invention is less likely to be on a support.
With one layer of an internal latent image type silver halide grain according to the present invention.
In addition to having a photosensitive emulsion layer containing, a filter layer, an intermediate layer,
Various protective layers, undercoat layers, backcoat layers, antihalation layers, etc.
It is possible to provide a large number of photographic constituent layers. When the photographic light-sensitive material of the present invention is used for full color,
At least one layer of red-sensitive silver halide emulsion on carrier
Layer, green-sensitive silver halide emulsion layer and blue-sensitive halogenated
A silver emulsion layer is applied. At this time, at least one layer of photosensitivity
-Sensitive silver halide emulsion layer is an internal latent image type halogen according to the present invention.
Silver halide grains as long as they contain silver halide grains.
An internal latent image type halogenated silver halide emulsion layer according to the present invention is used.
It preferably contains silver particles. Also each photosensitivity
Two or more silver halide emulsion layers, even if they have the same color sensitivity
May be separated into layers with different sensitivities.
If at least one layer has the same color sensitivity,
It contains an internal latent image type silver halide grain according to the invention.
However, the internal latent image type may be used in the present invention for all emulsion layers.
It preferably contains silver halide grains. The photographic light-sensitive material according to the present invention is used for general black and white, X ray,
For color, false color, printing, infrared, micro,
It can be effectively applied to various uses such as silver dye bleaching.
Colloid transfer method, silver salt diffusion transfer method, Rogers
U.S. Patents 3,087,817, 3,185,567 and 2,983,60
No. 6, U.S. Pat. No. 3,253,915 to Weyerts et al., White
U.S. Pat. No. 3,227,550 to Mohr et al. U.S. Pat.
27,551, US Patent 3,227,552 to Whitemore et al. And
U.S. Pat.Nos. 3,415,644, 3,415,645 and Rand et al.
Color image transfer as described in 3,415,646
Method, color diffusion transfer method.

【The invention's effect】

By using the internal latent image type silver halide emulsion peculiar to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having a sufficiently high maximum density and a sufficiently low minimum density and excellent storage stability. You can

【Example】

Hereinafter, the present invention will be illustrated with reference to examples, but the embodiments of the present invention are not limited thereto. Example-1 A silver chlorobromide emulsion EM-1 was prepared using the following five types of solutions. The seed emulsion is a monodisperse silver chlorobromide emulsion and has an average grain size of 0.27 μm. (Solution A-1) Ocein gelatin 31.4 g Distilled water 1285 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% Ethanol solution 2.8 ml 28% Ammonia water 18.9 ml Emulsion 0.1287 mole equivalent (Solution B-1) AgNO ₃ 218.1g 28% ammonia water 182.1ml Make up to 641.6ml with distilled water. (Solution C-1) KBr 152.7 g Make up to 641.6 ml with distilled water. (Solution D-1) Amount necessary to adjust pAg of an aqueous solution containing 119.0 g of KBr in 1000 ml of solution (Solution E-1) Amount required to adjust pH of a 56% acetic acid solution at 40 ° C. JP-A-57-92523 and 57-92524 Solution A-1 to solution B-1 and solution C-1 using the mixing stirrer shown in
And were added by the simultaneous mixing method so that a time during which no fine particles were generated was generated. The pAg, pH and rate of addition of solution B-1 during co-mixing were controlled as shown in Table-1. The pAg and pH were controlled by changing the flow rates of solution D-1 solution E-1 and solution C-1 by a roller tube pump with variable flow rate. Two minutes after the addition of the solution B-1 was completed, the pH was adjusted to 6.0 with the solution E-1. Next, deionized water was washed by a conventional method, and ossein gelatin 3
Disperse in an aqueous solution containing 5.2 g, then add distilled water to a total volume of 1000 m
adjusted to l. The obtained emulsion is designated as EM-1. EM-1 obtained above was divided, and 3.2 mg of sodium thiosulfate (pentahydrate) was added to 1 mol of silver and aged for 70 minutes at 60 ° C. The obtained emulsion is designated as EM-2. On the other hand, to another part of EM-1, 3.2 mg of sodium thiosulfate (pentahydrate) and 0.96 mg of potassium chloroaurate were added to 1 mol of silver, and chemical sensitization was performed at 60 ° C. for 70 minutes. The obtained emulsion is designated as EM-3. A silver bromide core / shell type emulsion EM-4 was prepared using the EM-2 obtained above as a core emulsion and the following 5 kinds of solutions. (Solution A-4) Ocein gelatin 16.73 g Distilled water 965.6 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% Ethanol solution 2.8 ml 28% Ammonia water 18.9 ml Seed emulsion (EM-2) 0.5957 mol equivalent (Solution B-4) AgNO ₃ 138.8g 28% Ammonia water 115.8ml Distilled water to 408.1ml (Solution C-4) KBr 97.13g Distilled water to 408.1ml (Solution D-4) KBr119 in 1000ml of solution Aqueous solution containing 0.0 g pAg adjustment required amount (Solution E-4) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C., a solution A was prepared using a mixing stirrer disclosed in JP-A-57-92523 and 57-92524. -4 to solution B-4 and solution C-
4 and 4 were added by the simultaneous mixing method, taking a time such that fine particles were not generated on the way. The pAg · pH during the simultaneous mixing and the addition rate of the solution B-4 were controlled as shown in Table-2. pAg
The pH was controlled by changing the flow rates of solution D-4, solution E-4 and solution C-4 by a roller tube pump with variable flow rate. Two minutes after the addition of the solution B-4 was completed, the pH was adjusted to 6.0 with the solution E-4. Next, deionized water was washed by a conventional method, and ossein gelatin 3
Disperse in an aqueous solution containing 5.2 g, then add distilled water to a total volume of 1000 m
adjusted to l. The obtained emulsion is designated as EM-4. EM-5 was prepared in the same manner as EM-4. However, the solution A-5 was used instead of the solution A-4, and the solution C-5 was used instead of the solution C-4. (Solution A-5) Ocein gelatin 16.73 g Distilled water 965.6 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% Ethanol solution 2.8 ml 28% Ammonia water 18.9 ml 4-Hydroxy-6-methyl-1,3 , 3a-Tetraazaindene 84.4 mg seed emulsion (EM-2) 0.5957 mol equivalent (Solution C-5) KBr 97.13 g 4-hydroxy-6-methyl-1,3,3a-tetraazaindene 115.6 mg with distilled water Make 408.1 ml. EM-6 was prepared in the same manner as EM-4. However, instead of the seed emulsion (EM-2) and the equivalent amount of 0.5957 mol in A-4, the seed emulsion (EM-3) and the equivalent amount of 0.5957 mol were used, and the other procedure was the same as that of EM-4. EM-7 was prepared in the same manner as EM-5. However, instead of the seed emulsion (EM-2) and 0.5957 mol equivalent in solution A-5, the seed emulsion (EM-3) and 0.5957 mol equivalent were used, and other than that, EM
Same as -4. To the four emulsions EM-4, EM-5, EM-6 and EM-7 obtained above, 2.2 mg of sodium thiosulfate (pentahydrate) and 1.5 mg of potassium chloroaurate were added per mol of silver. Then, chemical sensitization was performed at 50 ° C for 90 minutes. The four kinds of emulsions thus obtained were each added with a conventional extender and a hardener, and then coated and dried on a cellulose triacetate support so that the coated silver amount was 35 mg / 100 cm ^2. Samples 1 to 4 were obtained. Some of these coated samples were stored for 3 days under the conditions of a temperature of 27 ° C and a relative humidity of 60% (condition-1), and another part was stored at a temperature of 50%.
It was stored for 3 days under conditions of ° C and 80% relative humidity. (Condition-2) These samples were exposed using a sensitometer through an optical wedge for sensitization (hereinafter referred to as wedge exposure), developed with a developer having the following formulation at 20 ° C for 4 minutes, and then washed with water, fixed and washed with water. , Dried. Phenidone 0.4 g Sodium sulfite (anhydrous) 75.0 g Hydroquinone 10.0 g Sodium carbonate (monohydrate) 40.0 g Potassium bromide 4.0 g 5-Methylbenztriazole 10.0 mg 1-Formyl-2-phenylhydrazine (fogging agent) 0.1 g Water In addition, 1 (pH was adjusted to 12.5 with sodium hydroxide.) Table 3 shows the results of measuring the sensitivity, the maximum density (Dmax) and the minimum density (Dmin) of the obtained positive image. However, the sensitivity was represented by the relative value of the reciprocal of the exposure amount giving a density of (Dmax + Dmin) / 2. From the results shown in Table 3, it can be seen that the emulsion of the present invention has high sensitivity and sufficiently high maximum density, and that even under conditions of high temperature and high humidity, the maximum density is decreased, the minimum density is increased, and the sensitivity fluctuation is small. . Example-2 A silver chlorobromide emulsion EM-8 was prepared using the following 5 kinds of solutions. The seed emulsion is a monodisperse silver bromide emulsion with an average grain size of 0.27μ.
m. (Solution A-8) Ocein gelatin 30.8 g Distilled water 1258.6 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% Ethanol solution 2.8 ml 28% Ammonia water 18.92 ml Seed emulsion (EM-2) 0.1670 mol equivalent (Solution B-8) 211.6 g AgNO ₃ 28% ammonia water 176.6 ml Distilled water to 622.4 ml. (Solution C-8) NaCl 7.28 g KBr 133.3 g Distilled water to 622.4 ml (Solution D-8) An aqueous solution containing 56.5 g of NaCl and 4.1 g of KBr in 1000 ml of solution
pAg adjustment required amount (solution E-8) 56% acetic acid aqueous solution pH adjustment required amount Solution A-8 was added to solution B-8 at 40 ° C using the mixing stirrer disclosed in JP-A-57-92523 and 57-92524. 8 and 8 were added by the simultaneous mixing method so that a time during which no fine particles were generated was required. The pAg · pH and the addition rate of solution B-8 during the simultaneous mixing were controlled as shown in Table 4. The pAg and pH can be controlled by the solution D-8 using a roller tube pump with variable flow rate.
This was performed while changing the flow rates of the solution E-8 and the solution C-8. Two minutes after the addition of the solution B-8 was completed, the pH was adjusted to 6.0 with the solution E-8. Next, deionized water was washed by a conventional method, and ossein gelatin 35.2
After being dispersed in an aqueous solution containing g, the total amount was adjusted to 1000 ml with distilled water. The obtained emulsion is designated as EM-8. Using the EM-8 obtained above as a core, a silver chlorobromide emulsion EM-9 was prepared using the following four types of solutions. (Solution A-9) Ocein gelatin 14.2g Distilled water 904.3ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 2.8ml Seed emulsion (EM-8) 0.6849 mole equivalent (Solution B-9) AgNO ₃ 123.6g Make up to 363.5ml with distilled water. (Solution C-9) NaCl 21.27g KBr 43.26g Distilled water to 363.5ml (Solution D-9) Aqueous solution containing NaCl 58.1g and KBr 0.8g in 1000ml solution pAg adjustment required amount 60 ° C No. 57-92523 and No. 57-92524 are used.The solution A-9 is mixed with the solution B-9 and the solution C-9 by using the mixing and stirring method. Was added. PAg / pH and solution B-9 during simultaneous mixing
The addition rate of was controlled as shown in Table-5. The pAg was controlled by changing the flow rates of the solution D-9 and the solution C-9 using a roller tube pump with a variable flow rate. Next, deionized water was washed by a conventional method, and ossein gelatin 35.2
After being dispersed in an aqueous solution containing g, the total amount was adjusted to 1000 ml with distilled water. The obtained emulsion is designated as EM-9. EM-10 was prepared similarly to EM-9. However, solution A-10 was used in addition to solution A-9, and solution C-10 was used in addition to solution C-9. Other than that, it carried out like EM-9. (Solution A-10) Ocein gelatin 14.2g Distilled water 904.3ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 2.8ml 4-hydroxy-6-methyl-1,3,3a, 7-tetra Zaindene 58.2 mg Seed emulsion (EM-8) 0.6849 mol equivalent (Solution C-10) NACl 21.27 g KBr 43.26 g 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 61.8 mg Distilled water To 363.5 ml. Furthermore, using the following five types of solutions, silver chlorobromide emulsion EM-1
1 was prepared. The seed emulsion is a monodisperse silver bromide emulsion with an average grain size of 0.2.
It is 7 μm. (Solution A-11) Ocein gelatin 28.87g Distilled water 1260.0ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% Ethanol solution 2.8ml 28% Ammonia water 18.92ml Emulsion 0.1670mol equivalent (Solution B-11 ) AgNO ₃ 211.6g Make up to 622.4ml with distilled water. (Solution C-11) KI 2.07g NaCl 50.9g KBr 43.0g Distilled water to 622.4ml (Solution D-11) Aqueous solution containing 58.4g NaCl and 0.2g KBr in 1000ml solution pAg adjustment required amount (Solution E -11) 56% Acetic Acid Aqueous Solution At a required amount of pH adjustment at 40 ° C, Solution A-11 was added to Solution B-11 using the mixing stirrer disclosed in JP-A-57-92523 and 57-92524.
And were added by the simultaneous mixing method so that a time during which no fine particles were generated was generated. The pAg · pH during the simultaneous mixing and the addition rate of the solution B-11 were controlled as shown in Table-6. pAg
The pH was controlled by changing the flow rates of solution D-11, solution E-11, and solution C-11 by a roller tube pump with variable flow rate. Two minutes after the addition of solution B-11 was completed, the pH was adjusted to 6.0 with solution E-11.
Adjusted to. Next, deionized water was washed by a conventional method, and ossein gelatin 35.2
After being dispersed in an aqueous solution containing g, the total amount was adjusted to 1000 ml with distilled water. The obtained emulsion is designated as EM-11. Using the EM-11 obtained above as a core, a silver chlorobromide emulsion EM-12 was prepared using the following four types of solutions. (Solution A-12) Ocein gelatin 9.37g Distilled water 787.2ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 2.8ml Seed emulsion (EM-11) 0.8554 mole equivalent (Solution B-12) AgNO ₃ 94.6g Make up to 278.2 ml with distilled water. (Solution C-12) NaCl 3.26g KBr 59.6g Make up to 278.2 ml with distilled water. (Solution D-12) Aqueous solution containing 55.3 g of NaCl and 6.5 g of KBr in 1000 ml of solution pAg adjustment required amount Solution at 60 ° C using a mixing stirrer disclosed in JP-A-57-92523 and 57-92524. A-12 solution B-12 solution C-12
And were added by the simultaneous mixing method so that a time during which no fine particles were generated was generated. The pAg · pH during the simultaneous mixing and the addition rate of the solution B-12 were controlled as shown in Table 7. pAg
The pH was controlled by changing the flow rates of the solution D-12 and the solution C-12 with a roller tube pump having a variable flow rate. Next, deionized water was washed by a conventional method, and ossein gelatin 35.2
After being dispersed in an aqueous solution containing g, the total amount was adjusted to 1000 ml with distilled water. The obtained emulsion is designated as EM-12. Separately, a silver chlorobromide emulsion is prepared by using the following five kinds of solutions.
EM-13 was prepared. The seed emulsion is a 0.27 μm monodisperse silver bromide emulsion. (Solution A-13) Ocein gelatin 28.87g Distilled water 1260.0ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 2.8ml 4-hydroxy-6-methyl-1,3,3a, 7-tetra Azaindene 9.5 mg Potassium hexalochloroiridate 18 × 10 ^-9 mol 28% ammonia water 18.9 ml Emulsion 0.1670 mol equivalent (Solution B-13) AgNO ₃ 211.6 g 28% ammonia water 176.6 ml Distilled water to 622.4 ml To do. (Solution C-13) KI 2.07 g NaCl 50.9 g KBr 43.0 g 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 70.5 mg Distilled water to 622.4 ml. (Solution D-13) Aqueous solution containing 58.4 g of NaCl and 0.2 g of KBr in 1000 ml of solution pAg adjustment required amount (Solution D-14) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C., JP-A-57-92523 and Solution A-13 and solution C-13 using the mixing stirrer shown in No. 57-92524.
13 and 13 were added by the simultaneous mixing method, taking a time such that fine particles were not generated on the way. The pAg · pH during the simultaneous mixing and the addition rate of the solution B-13 were controlled as shown in Table-8. pA
The g and pH were controlled by changing the flow rates of solution D-13, solution E-13, and solution C-13 by a roller tube pump with variable flow rate. Two minutes after the addition of the solution B-13 was completed, the pH was adjusted to 6.0 with the solution E-13. Next, deionized water was washed by a conventional method, and ossein gelatin 35.2
After being dispersed in an aqueous solution containing g, the total amount was adjusted to 1000 ml with distilled water. The obtained emulsion is designated as EM-13. Using the EM-13 obtained above as a core, a silver chlorobromide emulsion EM-14 was prepared using the following four types of solutions. (Solution A-14) Ocein gelatin 9.37g Distilled water 787.2ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 2.8ml 4-hydroxy-6-methyl-1,3,3a, 7-tetra Zaindene 36.3 mg seed emulsion (EM-13) 0.8554 mol equivalent (Solution B-14) AgNO ₃ 94.6 g Distilled water to 278.2 ml. (Solution C-14) NaCl 3.26 g KBr 59.6 g 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 23.7 mg Distilled water to 278.2 ml. (Solution D-14) Aqueous solution containing 55.3 g of NaCl and 6.5 g of KBr in 1000 ml of solution pAg adjustment required amount Solution at 60 ° C using a mixing stirrer disclosed in JP-A-57-92523 and 57-92524. Solution B-14 and solution C- in A-14
14 and 14 were added by the simultaneous mixing method, taking a time such that no fine particles were generated on the way. PAg and solution B during co-mixing
The addition rate of -14 was controlled as shown in Table-9. The pAg is controlled by the solution D-14 using a roller tube pump with variable flow rate.
And the flow rate of the solution C-14 was changed. Next, deionized water was washed by a conventional method, and ossein gelatin 35.2
After being dispersed in an aqueous solution containing g, the total amount was adjusted to 1000 ml with distilled water. The obtained emulsion is designated as EM-14. A sensitizing dye represented by the following formula was added to each of the four types of emulsions EM-9, EM-10, EM-12, and EM-14 obtained above. The magenta coupler 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecylsuccinimidoanilino) -5-pyrazolone was dissolved in dibutyl phthalate and ethyl acetate and dispersed in a gelatin aqueous solution. A prepared emulsifier was prepared. Next, this emulsion dispersion was added to and mixed with each of the above emulsions, a hardener was added, and the amount of coated silver was coated on a range-coated paper support so that the coated silver amount was 6.7 mg / 100 cm ² , followed by drying. 5-8
I got it. In addition to EM-9, the above-mentioned coupler emulsion dispersion was added separately, and further 4-hydroxy-6-methyl-1,3,3 was added.
50 mg of a, 7-tetraazaindene per 100 mol of silver, 100 m
g, 200 mg, and 400 g were added to each, and a hardener was also added, and samples coated and dried in the same manner were also added to prepare samples 9 to 12. These samples were wedge-exposed through a yellow filter and developed with a developer having the following formulation at 30 ° C. for 3 minutes. 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.0 g Sodium sulfite (anhydrous) 2.0 g Sodium carbonate (monohydrate) 15.0 g Potassium bromide 1.0 g Benzyl alcohol 10 ml of water was added to 1 (pH was adjusted to 10.2 with sodium hydroxide) However, 20 seconds after the start of development, the entire surface was uniformly exposed with white light of 0.6 lux for 20 seconds. Then, it was washed with water, bleached, fixed, washed with water and dried. (Process-1) Process-2 and process-3 were performed in the same manner as process-1. However, instead of uniformly exposing the entire surface with the 0.6 lux white light obtained in Treatment-1, the entire surface was uniformly exposed with 0.3 lux (Treatment-2) and 0.15 lux (Treatment-3) white light. Table 10 shows the results of measuring magenta-positive images of the samples obtained in the above-mentioned Treatment-1 to Treatment-3. As can be seen from the results shown in Table 10, the emulsion samples of the present invention can obtain good images with sufficiently large maximum density and small minimum density, and are stable against fluctuations in illuminance during overall exposure. Recognize. It is also found that the effect of the present invention cannot be obtained even if an azaindene compound is present during coating.

Continuation of the front page (56) Reference JP 60-122935 (JP, A) JP 55-144238 (JP, A) JP 59-86040 (JP, A) JP 58-212143 (JP , A) JP 54-99419 (JP, A) JP 60-247237 (JP, A)

Claims (1)

[Claims] 1. A grain surface having at least one silver halide emulsion layer containing an internal latent image type silver halide grain which is not previously fogged, and after image exposure, after fog treatment and / or fog. In a photographic light-sensitive material in which a positive image can be directly obtained by surface development while performing a treatment, a novel silver halide in which at least a part of the internal latent image type silver halide grain composition is a mixture of an ammine silver complex salt and a soluble halide. A compound represented by the following general formula (I), (II), (III), or (IV) after the growth process by precipitation and the constitution of the internal latent image type silver halide grains and the following general formula ( A direct positive silver halide photographic light-sensitive material, which is produced in the presence of at least one compound selected from compounds having a repeating unit represented by V). General formula (I) General formula (II) General formula (III) General formula (IV) General formula (V) [In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each is 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,
Amino group derivative, halogen atom, cycloalkyl group,
It represents a derivative of a cycloalkyl group, an aryl group, or a derivative of an aryl group. ), 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 (I), (II), (III) or ( I
It represents a monovalent group obtained by removing one hydrogen atom from the compound represented by V), and J represents a divalent linking group. ]