JP2729485B2 - Silver halide photographic emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is excellent in granularity with high sensitivity, has good raw storage stability and stability of latent images, has little dependence on exposure time, and has a low development progress. The present invention relates to a silver halide photographic emulsion which is of a parallel movement type, has a small gradation variation and can be processed quickly, and particularly relates to a photosensitive material which is excellent in production stability and uniformity of finished quality.

(Prior Art) With the widespread use of silver halide light-sensitive materials, there is a demand that anytime, anywhere, quickly and easily obtain a high-quality image stably with a high shooting success rate.

Generally, it is known that a silver iodobromide photographic emulsion having an average silver iodide content of about 4 to 20 mol% is used for a high-sensitivity light-sensitive material such as a photographic light-sensitive material. Silver iodobromide photographic emulsions, especially those having a high silver iodide content, are advantageous for obtaining high-sensitivity and high-quality images. Special measures are required to obtain stability and excellent reciprocity failure characteristics.

In general, silver chloride, silver chlorobromide and silver iodochlorobromide photographic emulsions having a high average silver chloride content (for example, 30 mol% to 100 mol%) used in black-and-white printing paper and color print photosensitive materials are developed. Although it is advantageous for speeding up processing, high sensitivity,
Not only are there problems such as high-quality images, progression of development gradation and fog suppression, but also many problems such as raw storability, stability of latent images, and reciprocity failure characteristics. Further, a silver halide photographic emulsion having a low average silver iodide content of, for example, 4 mol% to 0 is advantageous for rapid stabilization of the desilvering step, particularly when used in a color light-sensitive material, but can provide a high quality image. Has difficulties.

For a silver halide photographic emulsion containing silver halide grains having a (100) plane, a CR-compound (a halogen conversion inhibitor or a chemical sensitization inhibitor) is preferably used during or before the chemical sensitization step. It has been found that the use of a vertex-developed silver halide (CDG) photographic emulsion improves these characteristics comprehensively. For example, it is described in Japanese Patent Application No. 61-311131 and related patent specifications.

A photographic emulsion containing silver halide grains having a (111) plane is conventionally easily obtained mainly from a silver iodobromide emulsion and has many of the above-mentioned defects. The above-mentioned Japanese Patent Application No. 61-311131 does not disclose a method for solving the defect of the photographic emulsion.
Improvement method of various defects Normal crystal grains having a (111) plane, such as octahedral, tetrahedral or tabular grains, and tabular twin grains have been proposed. However, there is no mention or guarantee that it will always be comprehensively improved because it is affected by factors that are not covered.

For example, JP-A-60-147727, JP-A-60-147728, JP-A-52-153428, JP-A-54-155827, and JP-A-58-95337.
No. 58-113926, No. 59-133540, and
No. 57-82835, No. 58-108526, No. 59-48756, No. 61-210345, No. 55-26589, No. 60-196749
U.S. Pat.Nos. 4,434,226, 4,441,310, 4,443,048, 3,320,899, and 3,966.
No. 476, No. 431854, No. 4414306, No. 4490458
No. 4,301,533 and No. 4,183,756.

The silver halide grains contain, for example, grains having a (111) plane having an average silver chloride content of at least 30 mol%, preferably 50 mol%, with or without an average silver iodide content of 4 mol% or less. For example, Japanese Patent Application No. 61-
Nos. 144228, 61-144229 and 62-47225. Emulsions having such a halogen composition tend to exhibit many of the above-mentioned defects more easily than conventional silver iodobromide emulsions.

U.S. Pat. No. 3,628,960 and JP-A-55-26589 describe early stages of the formation of silver halide grains, e.g. in the first charge pot or before the formation of the grains reaches 85% mol. A method for producing a silver halide emulsion in which a sensitizing dye is present to enhance the efficiency of spectral sensitization and the adsorption of the sensitizing dye is disclosed. JP-A-59-133540 discloses a site where a low silver iodide content, for example, silver chloride is selected by using a site indicator of a sensitizing dye in a silver halide host grain opened by a (111) plane. Can be epitaxially grown. It also shows that sensitivity is improved by the epitaxial deposition of silver salts, such as silver chloride, with a limited iodide content on selected surface sites. Further usual chemical sensitization is described, for example, in Research Disclosure, 161176 (Jan.
February) No. 17643 states that it can be applied before or after epitaxial deposition.

Photosensitive materials with a multi-layer structure, especially color photosensitive materials, are required to have not only the set sensitivity and gradation, but also stability over all layers such as exposure temperature, time, latent image, and development progress, which is crucial to the finished quality. Affect. It is an object of the present invention to remedy these deficiencies.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic emulsion in which silver halide grains are dispersed in a dispersion medium, wherein the silver halide grains have a (111) plane. It is a normal crystal grain having no epitaxial growth site, and has a general formula (I) to (described later) during the chemical sensitization step or before the chemical sensitization step.
At least 50% of the silver halide grains prepared by adding at least one compound selected from the group consisting of the compound represented by [V] and nucleic acids, and having the (111) plane;
(Projected area): a) particles controlled to start development at or near the vertices of the ridges of the particles (vertical development type particles: CDG), and / or
Or b) a silver halide photographic emulsion characterized by being a grain controlled to start development at or near the ridge of the grain (ridge-developed type grain: EDG) and a photographic material using such an emulsion Achieved by

In a preferred embodiment of the present invention, the silver halide grains are normal crystal grains having a (111) plane, and are obtained by applying the (111) plane to a support and developing the coated silver halide grains. At least 50% (projected area) of silver halide grains contributing to image formation at any density between [maximum density-minimum density] x 3/4 and minimum density + 0.2 in the characteristic curve
Is a silver halide photographic emulsion wherein the a) grains and / or the b) grains are the grains.

The vertex-developing type grains (CDG) in the present invention means that when a photosensitive material obtained by coating an emulsion containing these grains on a support is subjected to development processing, development starts from the apex of the grains and / or in the vicinity thereof. Silver halide grains controlled as described above.

Similarly, a ridge-developing type grain (EDG) is such that when a photosensitive material obtained by coating an emulsion containing the grain on a support is subjected to development processing, development starts from the ridge of the grain and / or the vicinity thereof. Controlled silver halide grains.

Here, controlled development start point means that 70% or more, particularly preferably 90% or more, of the development start point is present at the vertices, ridges and / or the vicinity thereof.

As a method for specifying the location of the development start point, there is the following method. That is, a developer used for processing a light-sensitive material obtained by coating this photographic emulsion on a support is treated with a developing solution under a developing condition to obtain a silver image (maximum density-minimum density) .times.3 / 4 in a characteristic curve of the emulsion. Exposure corresponding to or 100
Double exposure is performed, development is started using a developer having substantially the same liquid composition ratio, and then stopped using a 5% aqueous solution of glacial acetic acid. And can be identified by observation with an electron microscope photograph of

Here, the vertex of the silver halide crystal and its vicinity or the ridge and its vicinity have a roundness in addition to a normal twinned tabular multiple twin such as an octahedron, a tetrahedron or a 24-hedron. Although there are particles, etc., it means a part or its vicinity that is substantially determined to be a vertex or a ridge on crystallography, and the vicinity is preferably about 1/3 of the diameter of a circle such as the area phase of a projected particle. Preferably within a circle centered at the apex with a radius of 1/4 length or within a rectangle formed by a line separated by about 1/3 and preferably 1/4 of the diameter of the ridge and the circle Means
More preferably, the length is about 1/5 of the diameter of the circle, and the effect is more remarkably exhibited.

The developer used for observing the starting point of development is preferably a developer having the same liquid phase composition ratio as a developer practically used for photosensitive materials using CDG or EDG particles. For example, it can be used by diluting it up to about 50 times to facilitate observation. The development temperature is preferably a practically practical temperature. As the developing solution for evaluation, a developing solution having the following composition ratio can be mentioned. That is, CDG or EDG can be evaluated using a developer having the following composition ratio.

(For color light-sensitive materials) Diethylenetriaminepentaacetic acid ... 1.0 g 1-hydroxyethylidene 1,1-diphosphonic acid ... 3.0 g Sodium sulfite ... 4.0 g Potassium carbonate ... 30.0 g Potassium bromide ... 1.4 g Potassium iodide… 1.5 mg Hydroxylamine sulfate… 2.4 g 3-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate… 4.5 g Add water ( pH adjusted to 10.05) ・ ・ ・ 1.0 (for black and white photosensitive material) Methol ・ ・ ・ 2.0g Sodium sulfite ・ ・ ・ 100.g Hydroquinone ・ ・ ・ 5.0g Borax 5 ・ H ₂ O ・ ・ ・ 1.53g Water (Adjust the pH to 8.60) ... 1000 ml In the emulsion of the present invention, it is essential that at least 50% (projected area) of all silver halide grains in the emulsion is CDG or EDG, but it is more preferable. More than 70% (projected area), especially Preferably, 80% or more (projected area) is CDG or EDG.

CDG or E in the silver halide emulsion of the present invention
The silver halide emulsion for which DG is observed is preferably tested for each lot manufactured by the same manufacturing process. In the case of mixed emulsions of different lots or types of silver halide emulsions, it is tested as a mixed silver halide emulsion, and if at least 50% of the projected area of the silver halide grains is CDG or EDG, Thus, it can be concluded that the effects of the present invention are remarkably exhibited. However, even at 50% or less, the silver halide emulsion before mixing satisfies the above-mentioned conditions, or the characteristic curve (maximum density-minimum Density) x 3/4 or minimum density +
With respect to silver halide grains contributing to image formation at any density between 0.2 and 0.2, at least the projected area of the developed grains is determined by a test method that specifies the location of a predetermined development start point.
If 50% of the particles are CDG or EDG, it can be determined that the effects of the present invention are exhibited.

In a CDG emulsion (emulsion composed of CDG) or an EDG emulsion (emulsion composed of EDG), vertex development and edge development may proceed in parallel or vertex development may proceed with priority. CDG emulsion or EDG
The essential features of the emulsion are the control of silver halide crystal formation (growth, ripening or halogen conversion) and chemical sensitization so that the starting point of development is selectively concentrated at a specific site on the surface of the silver halide grain. In addition, the starting point of the development of each silver halide grain contained in the emulsion of the simultaneous production lot may be controlled so as to concentrate on a specific site such as a vertex and / or a ridge. Conventionally, an indicator of the growth surface of a silver halide crystal is known, but a silver halide emulsion having such development characteristics and its excellent characteristics are not known. By controlling the development start point according to the present invention,
Several conventional said defects can be improved at the same time. This is a surprising finding. A factor related to the control of the development starting point of the CDG or EDG emulsion according to the present invention is firstly the crystal habit of silver halide grains. In the present invention, it is a particle having a (111) plane. If the particle has a (111) plane, the shape of the particle is not a major factor. However, particles that are usually easily obtained include substantially normal crystal grains, for example, octahedral, tetradecahedral, and tabular grains, such as multiple twin tabular grains and tabular bonded growth grains, and are preferably normal crystal grains. Second, there is a halogen composition of silver halide grains. When the composition of silver iodide or silver chloride changes, the photographic characteristics change as described above, and the viewpoint of defects, that is, problems to be improved changes. However, this problem can be ameliorated by the present invention. Probably because the nature of the problem is directly and indirectly related to the formation site and number of development centers and their selective concentration. Third, in the process of chemical sensitization, the formation of the surface of the silver halide grains and the location of the chemical sensitization reaction are controlled by the CR-compounds present on the surface of the silver halide grains to control the number and the number of photosensitive nuclei. That is. The CR-compound is adsorbed to silver halide grains during or before chemical sensitization, and chemical development is performed by controlling silver halide grain formation or halogen conversion so as to limit the position and number of development start points. It is called a compound that has the action of controlling It can be distinguished from the site indicator described in JP-A-59-133540 in that it does not act to determine the habit of silver halide grains. Preferably, the CR-compound is adsorbed after the grains have been formed, or after the grains have been formed, in an amount up to 85 mol% of the total silver halide grains and prior to chemical sensitization. Fourth is the developer used or the developing conditions. Since this is a factor defined as a method of developing the light-sensitive material used in the present invention, it is rather to find a silver halide emulsion exhibiting the above-mentioned characteristics under these processing conditions. Other factors will be apparent from the description of the examples.

Next, the silver halide photographic emulsion used in the present invention will be described. The silver halide photographic emulsion of the present invention comprises (11)
1) A photographic emulsion containing silver halide crystals (grains) having faces, preferably at least the entire surface of the silver halide grains.
30% are (111) planes. Particles with (111) planes can be found, for example, in The James of THJames, The theory of the Photographic Proces.
s Fourth Edition (Macmillan, published in 1977) 97 pages to 100
Pages, JP-A-58-85337, JP-A-58-113926, U.S. Pat.No. 4,434,226, JP-A-52-153428, JP-A-60-35726 and JP-A-58-108526. Have been.

The substantially normal crystal grains having a (111) plane according to the present invention are those in which at least 30%, preferably 50%, and more preferably 75% or more of the total outer surface area is composed of the (111) plane. Include an octahedron, a tetrahedron and the like. The term “substantially” refers to particles in which the peaks and ridges are visually recognized, and may be microscopically a twin plane, a transition plane, or a bonding plane. The particles of the present invention
Normal crystal grains are preferred over polymorphic so-called epitaxial grains produced by epitaxial growth. The particles of the present invention may have a uniform internal crystal structure, but may have different multi-structure particles. The air may have a high silver iodide content, between 20 and 40 mol%, with a lower silver iodide content layer on its outer shell.

The core may be a layer of silver bromide or silver iodobromide with a low silver iodide content and a layer of silver iodobromide with a higher silver iodide content, for example 10 to 40 mol%.

It is preferable that the outermost shell layer has a thin layer having a high silver iodide content. Further, a layer having a silver iodide content of 4 mol% or less in the core and a lower silver iodide content layer may be provided on the outer shell, or a thin silver iodide layer may be provided on the outermost shell. For these grains, the position and number of the development starting point of the present invention are selected by a method such as ripening due to the presence of a material having the property of a silver halide solvent due to the presence of a CR compound, growth of silver halide or conversion of halogen. It is preferred to form the surface of the particles in a controlled manner. It is preferred that a CR-compound coexist in this step.

Next, a grain having a (111) plane having a high silver chloride content will be described. The theory of the Pho
As described in the right run on page 98 of the book called tographic Process (1
11) It is necessary to devise to obtain halogenated grains with high silver chloride content. Octahedral particles composed of (111) planes are described, for example, in Claes et al., The journal Photographic Science 21.
Volume 39 (1973) and Wyrsh's International Congress
of Photographic Science III-13, p. 122 (1978).

JP-A-55-26589 discloses the production of octahedral particles using a merocyanine dye. This method provides favorable photographic properties due to enhanced dye adsorption.
However, the octahedron is limited to a specific dye structure, so when preparing a blue-sensitive emulsion, a green-sensitive emulsion, a red-sensitive emulsion, etc., it is necessary to give an absorption maximum at a specific wavelength or adjust the shape of the spectrum according to the purpose. In many cases, it is difficult to make the preparation.

Silver halide emulsions having a (111) plane having a high silver chloride content are more susceptible to fogging or reciprocity failure when chemically sensitized to obtain higher sensitivity than other emulsions. Further, there are defects such as instability of a latent image and large dependence of gradation on development progress, which are defects of a silver halide emulsion of high silver chloride.

Therefore, in the silver halide emulsion having a (111) plane having a high silver chloride content, the effect of the improvement according to the present invention is particularly large.

These normal crystal grains of the present invention localize a high silver bromide content using CR-compounds on or near the surface thereof. Alternatively, the above difficulty can be solved by providing a layer containing high silver bromide or a layer containing high silver iodide by halogen conversion and applying chemical sensitization. The compound represented by the following general formula [VI] can also be used to prevent fogging.

In the substantially normal crystal grains according to the present invention, silver halide grains having an average silver iodide content of 4 mol% or more, preferably 2 mol% or less, more preferably 1 mol% or less and containing substantially no silver halide are also useful. It is. These grains may be converted, for example, by adding iodide or bromide together with the CR-compound, or the surface may be grown in the presence of a solvent, particularly the CR compound and silver iodide, silver bromide or silver iodobromide grains. By carrying out ripening or conversion in the presence of fine grains or a solvent together with the fine grains or further subjecting them to chemical sensitization, silver halide grains suitable for the purpose of the present invention can be obtained.
Further, in the normal crystal grains, silver halide photographic emulsions containing grains having an average silver iodide content of 4 mol% or less and having a high silver chloride content and having a (111) face have many disadvantages. Only especially useful.

The halogen composition of the silver halide grains can be measured for each silver halide grain using an electron beam microanalyzer. This EPMA method is described in JP-A-60-143332.

In the present invention, the silver halide composition on the surface is XPS (x-r
ay Photoelectron Spectroscopy) by Shimadzu-dupon
It can be observed using ESCA750 type spectrometer manufactured by the company.

The measurement of the silver halide composition by the XPS method is described in "Surface Analysis", published by Kodansha (1977), co-authored by Someno and Yasumori.

As described above, the CDG emulsion and the EDG emulsion of the present invention can be prepared by making use of various element techniques known as a silver halide emulsion preparation method, and typical preparation methods are as follows.

After preparing host grains composed of (111) planes and adsorbing a CR compound on the main surface thereof, silver and halogen are newly supplied to grow silver halide mainly on the top and ridge portions, and then the chemical Sensitize.

The newly supplied silver and halogen may be supplied in the form of silver ions and halogen ions, or may be supplied in the form of silver halide microcrystal grains. The supply amount of silver halide is preferably 15% of the silver halide finally obtained.
It is preferably at most mol%.

Further, at this time, a solvent for silver halide may be present.

The host particles adsorbed with a specific CR compound are chemically sensitized.

As the CR compound used in such a method, the following general formula (I
Compounds represented by V) to (V) are preferred.

The CR-compound used in the present invention is a compound which preferably and selectively adsorbs to silver halide crystals, particularly to the (111) plane.

Nucleic acids or their derivatives, adenines, are useful as preferred natural substances.

 Next, other preferred CR compounds will be described.

In the formula, Z ₁₀₁ and Z ₁₀₂ each represent an atomic group necessary for forming a heterocyclic nucleus.

As the heterocyclic nucleus, a 5- or 6-membered ring nucleus containing a nitrogen atom and a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom as a hetero atom (even if a fused ring is further bonded to these rings) And a substituent may be further bonded).

Specific examples of the heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benzozine Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenin nucleus, indole nucleus, tetrazole nucleus, benzotellurazole nucleus, naphthoterazole nucleus and the like. it can.

R ₁₀₁ and R ₁₀₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. Each of these groups and the groups described below have the meaning including their substituents. For example, taking an alkyl group as an example,
It includes unsubstituted and substituted alkyl groups, which may be straight-chain, branched or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of the substituent of the substituted alkyl group include a halogen atom, a cyano group, an alkoxy group, a substituted or unsubstituted amino group, a carboxylic acid group, a sulfonic acid group, and a hydroxyl group. Or a plurality thereof may be substituted in combination.

Specific examples of the alkenyl group include a pinylmethyl group.

Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

m ₁₀₁ represents a positive number of 0 or 1, 2 or 3. m ₁₀₁
When R represents 1, R ₁₀₃ represents a hydrogen atom, a lower alkyl group, an aralkyl group, or an aryl group.

Specific examples of the aryl group include a substituted or unsubstituted phenyl group.

R ₁₀₄ represents a hydrogen atom. When m ₁₀₁ represents 2 or 3, R ₁₀₃ represents a hydrogen atom, R ₁₀₄ represents a hydrogen atom, a lower alkyl group, an aralkyl group, and can be connected to R ₁₀₂ to form a 5- or 6-membered ring. . When m ₁₀₁ represents 2 or 3, and R ₁₀₄ represents a hydrogen atom, R ₁₀₃ represents
In conjunction with R ₁₀₃ may form a hydrocarbon ring or a heterocyclic ring. These rings are preferably 5- or 6-membered rings. j ₁₀₁ and k ₁₀₁ represent 0 or 1, X ₁₀₁ represents an acid anion, and n ₁₀₁ represents 0 or 1.

In the formula, Z ₂₀₁ and Z ₂₀₂ have the same meaning as Z ₁₀₁ or Z ₁₀₂ described above. R ₂₀₁ and R ₂₀₂ have the same _meanings as R ₁₀₁ or R ₁₀₂ , and R ₂₀₃ represents an alkyl, alkenyl, alkynyl or aryl group. m ₂₀₁ represents 0, 1, or 2. R ₂₀₄ represents a hydrogen atom, a lower alkyl group or an aryl group. When m ₂₀₁ represents 2, R ₂₀₄ and R ₂₀₄ may be linked to form a hydrocarbon ring or a heterocyclic ring. These rings are preferably 5- or 6-membered rings.

 Q₂₀₁Is a sulfur atom, an oxygen atom, a selenium atom or N-
R₂₀₅Represents R₂₀₅Is R₂₀₃Is synonymous with j₂₀₁, R₂₀₁,
X₂₀₁ And n₂₀₁Is j₁₀₁, K₁₀₁, X₁₀₁ ^-And n₁₀₁
Is synonymous with

In the formula, Z ₃₀₁ represents an atomic group necessary for forming a heterocyclic ring. As the heterocycle, those described for Z ₁₀₁ and Z ₁₀₂ and specific examples thereof include other thiazolidine, thiazoline, benzothiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, dihydropyridine, dihydroquinoline, and benzine. Examples include nuclei such as imidazoline and naphthoimidazoline. Q ₃₀₁ is synonymous with Q ₂₀₁ . R ₃₀₁ has the same _meaning as R ₁₀₁ or R ₁₀₂ , and R ₃₀₂ has the same _meaning as R ₂₀₃ . m ₃₀₁ has the same _meaning as m ₂₀₁ . R ₃₀₃ Other synonymous with R _204, may form a hydrocarbon ring or a heterocyclic ring linked and the R ₃₀₃ and the other R ₃₀₃ when m ₃₀₁ represents 2 or 3. j ₃₀₁ represents the same meaning as j _101.

Next, specific examples of sensitizing dyes as CR compounds used in the present invention will be given. However, it is not limited to this.

PTS ^1- is p-toluenesulfonic acid anion It is.

PTS is p-toluenesulfonic acid anion It is.

In the present invention, particularly preferred CR for the (111) plane
-The compound is a compound represented by the following general formula [IV] or [V].

In the formula, Y represents a sulfur atom or an oxygen atom, and Z ¹ represents an atom group necessary for forming a saturated or unsaturated heterocyclic ring together with the sulfur atom or the oxygen atom, and the heterocyclic ring has a substituent. Is also good.

Here, atomic group represented by Z ¹ is formed of carbon atoms, nitrogen atom, oxygen atom, sulfur atom, a heterocyclic ring formed by Z ¹ and Y are 3-8 membered heterocyclic ring, this heterocyclic ring May be condensed with another ring to form a condensed ring.

Specifically, Thiiran, Thietane, Chian, Thiepin,
Thiosine, dihydrothiolane, thiophene, dihydrothiopyran, 4H-thiopyran, 2H-thiopyran, 1,3-thiaziridine, 1,3-thiosazolidine, oxazole, thiazole, 1,3-oxathiolane, 1,3-dithiolane, 1,
3-dithiolane, 1,3-dithiolene, 1,4-oxathiane, 1,4-diazane, 1,3-thiazane, benzothiolane,
Benzothian, benzothiaziridine, benzosaxathian and the like can be mentioned.

Specific examples of the substituent of the heterocyclic ring formed from Z ¹ and Y include a halogen atom and an alkyl group (preferably having 1 to 1 carbon atoms).
20), an aryl group (preferably having 6 to 20 carbon atoms), an alkoxy group (preferably having 6 to 20 carbon atoms), an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, an amino group, An amide group,
Ureido group, carboxy group, carbon ester group, oxycarbonyl group, carbamoyl group, acyl group, sulfo group, sulfonyl group, sulfinyl group, sulfonamide group, sulfamoyl group, cyano group, hydroxy group, nitro group, oxo group, thioxo group , An imino group and a selenoxo group.

Here, when there are two or more substituents, they may be the same or different.

Further, among the compounds represented by the general formula [IV], preferred are the following general formulas [IV '] or [IV "]
Can be represented by

In the formula, Z ² represents an atomic group necessary for forming a 5- or 6-membered saturated or unsaturated heterocyclic ring together with Y, a carbonyl group or a thiocarbonyl group, and this heterocyclic ring may have a substituent. Good. Here atomic group represented by Z ² and Z ² and Y
And the substituent of the heterocyclic ring formed from the carbonyl group or the thiocarbonyl group means the same as the substituent of the heterocyclic ring formed by Z ¹ and Z ¹ and Y represented by the general formula [IV].

n represents 1-3. When n is 2 or 3, each carbonyl group may or may not be adjacent.

Specific examples of the 5- or 6-membered saturated or unsaturated heterocyclic ring represented by the general formula [IV '] include the following. Specifically, there can be mentioned the compounds described on pages 20 to 29 of JP-A-63-25643 and Japanese Patent Application No. 62-47225.

For example Such.

Of the compounds represented by the general formula [IV '], those having a carbonyl group linked to a sulfur atom and those having a saturated heterocyclic ring are particularly preferred.

Specific examples of the compound of the present invention represented by the general formula [IV '] or the general formula [IV "] are shown below.

Further, the same occurs with respect to the ridges in the tabular grains of the EDG emulsion. That is, in the grain formation process, for the multi-structure particles using the CR compound for the (111) plane, the development center can be concentrated on the ridge or near the ridge by using the CR compound, and the development can be accelerated. Particularly preferred CR compounds
That is, a compound represented by the following general formula [V] is used.

The general formula [V] R ₁ -S- (V) _m -Y-R ₂ X is a divalent organic group, and alkylene, arylene,
_{Alkenylene, -SO 2 -, - SO -} , - O -, - S-, Are used alone or in combination. Alkylene, arylene, and alkenylene may have a substituent. The substituent is the same as the substituent described for R ₁ .

R ₃ is a hydrogen atom, an alkyl group, or an aryl group.

 m is 0 or 1.

R ₁ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
Preferred examples of R ₁ are a hydrogen atom and a substituted or unsubstituted alkyl group. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonyl group, a sulfonamide group, an amide group, an acyl group, a sulfamoyl group, a carbamoyl group, a ureido group, an alkoxycarbonylamino group, and an aryloxy group. Carbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonylthio group, alkylcarbonylthio group, arylcarbonylthio group, cyano group, hydroxy group, mercapto group, carboxy group,
Examples include a sulfo group, a nitro group, an amino group, an alkylthio group, an arylthio group, and a heterocyclic group.

R ₂ represents a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, an alkoxy group, or an aryloxy group. As a substituent, R ₁
The same as is possible. Preferred examples of R ₂ are a hydroxy group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted amino group.

Y in the general formula [V], represents a -CO or -SO _2, preferably -CO.

The total number of carbon atoms of the organic group of X, R ¹ , R ² or R ³ including the substituent is preferably 20 or less.

Specific examples of the compound represented by the general formula [V] used in the present invention are shown below, but the scope of the present invention is not limited to these compounds. Specific examples of this CR-compound are described on pages 10 to 14 of Japanese Patent Application No. 61-186481 and on pages 32 to 36 of Japanese Patent Application No. 62-47225.

The compound of the present invention represented by the general formula [IV] or [IV '] may be added at any time until the completion of the particle formation. Particularly preferably, it is present during or after the outer shell of the particles.

The CR represented by the general formulas (I) to (III) of the present invention
The compound is preferably used in the presence of the compound represented by any of formulas [IV] to [V], and also during conversion or grain formation or before chemical sensitization.

The CR represented by the general formulas (I) to (III) of the present invention
The compound is dissolved in an alcohol such as methanol or a water-miscible organic solvent such as ethyl acetate and added to the above-mentioned host silver halide emulsion. Alternatively, they may be added after being dispersed in an aqueous gelatin solution or an aqueous surfactant solution. The addition amount is preferably from 10 ^-6 to 10 ^-2 mol, more preferably from 10 ^-5 to 10 ^-3 mol, per mol of the host silver halide. Next, fine grain silver halide grains as described above are mixed,
The conversion can be completed by aging at a temperature in the range of 30 to 80 ° C. and a silver ion concentration in the range of pAg 5 to 10 as appropriate.

The compounds represented by the general formulas [IV] to [V] of the present invention can be used in a similar manner in an amount of 2 × 10 ^-5 to 3 × 10 ^-1 mol per mol of silver halide. Especially 2 × 10 ^-4
Mol to 1 × 10 ^-1 mol are used.

The CR-compound according to the present invention is adsorbed and developed on the silver halide surface before or during the silver halide grain formation, (including physical ripening), the halogen conversion process on the silver halide surface or chemical sensitization. A compound whose start site and number can be controlled. The adsorption surface for the (111) plane is important, and the appropriate amount is usually 10% or more, preferably 20% or more of the monomolecular saturated adsorption amount. It is preferable to use an amount which does not show other disadvantageous defects such as a decrease in sensitivity and development progress.

The preferred amount of use is 70% or more of the amount of monomolecular saturated adsorption on the surface of the silver halide when added, and is characterized in that it is larger than the amount used for other conventional functions. The CR compound is preferably adsorbed on silver halide formed at least 85 mol%, preferably at least 90 mol% of the total silver halide.

When a CR-compound is added during the formation of silver halide grains or in the process of halogen conversion, particularly in the case of halogen conversion, if the element ions or bromide ions are supplied at an excessively high concentration, the CR-compound according to the present invention may be used. The effect decreases relatively. Therefore, it is preferable that iodine ions and bromine ions are supplied slowly at a relatively low concentration.

A supplier whose supply rate can be controlled with a water-soluble halide such as potassium iodide or potassium bromide, for example, an organic halogen compound, an inorganic halogen compound having an appropriate solubility in water, or a halogen compound in which a capsule film is covered with a semi-permeable film. Etc. can be used. Practically, silver halide having finer grains than host grains and having a higher content of silver iodide or silver bromide than host silver halide is preferred. For example, the emulsion containing the host silver chloride particles to which the above-mentioned CR compound was adsorbed was mixed with an emulsion containing silver bromide fine particles having an average particle size of about 0.1 μm equivalent to about 1 mol% of the host silver chloride to cause conversion. Upon ripening, the silver bromide grains dissolve and disappear, and after reaching equilibrium, a layer having a new halogen composition is formed on the surface of the host grains, and the reaction stops. In parallel with the precipitation of the silver bromide phase formed at this time, as a result of the homogenization of the halogen composition, the outer surface of the silver bromide has a stable composition such as only about 3 mol% of silver bromide. You can get.

When iodine ions or bromine ions are rapidly added, it is preferable to make the halogen composition uniform in the preceding period by coexisting a solvent for silver halide together with the CR compound.

Probably during the conversion process, at least silver chloride and silver bromide are mixed by repeating dissolution and recrystallization, and silver bromide is diffused to some extent inside the grains.

In the process of forming silver halide grains, the effect of the CR compound can be enhanced by controlling the supply rate of silver ions and halide ions or by the presence of a solvent for silver halide.

In addition, it is important to select a chemical sensitizer and its use so as to suppress the chemical sensitization reaction by the adsorption of the CR-compound.

A silver halide solvent may be used during the growth or physical ripening of the grains, particularly during the production of the silver halide grains of the present invention.

Examples of frequently used silver halide solvents include thiocyanates, thioethers and thioureas, and ammonia can also be used in combination as long as it does not cause adverse effects.

For example, thiocyanates (U.S. Pat. Nos. 2,222,264, 2,448,534, and 3,320,069) and thioether compounds (for example, U.S. Pat. Nos. 3,271,157 and 3,574,628)
No. 3,704,130, No. 4,297,439, No. 4,276,34
No. 7, etc.), thione compounds (for example, JP-A-53-144319)
Nos. 53-82408 and 55-77737), amino compounds (for example, JP-A-54-100717) and the like.

In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may coexist. Particularly, an iridium salt or a rhodium salt is preferable.

It is added during the production of the silver halide grains of the present invention to accelerate grain growth. A method of increasing the addition speed, amount and concentration of a silver salt solution (eg, an AgNO ₃ aqueous solution) and a halide solution (eg, an NaCl aqueous solution) is preferably used.

Regarding these methods, for example, U.S. Pat.
No. 3,672,900, No. 3,650,757, No. 4,
No. 242,445, JP-A-55-142329, JP-A-55-158124, and JP-A-5-158124.
8-113927, 58-113928, 58-111934, 58
Reference can be made to the description of -111936 and the like.

CDG and / or EDG emulsions having silver halide grains having (111) planes according to the present invention can be used for the conversion of silver halide grains on the surface of silver halide grains, the growth of silver halide, An emulsion obtained by ripening and controlling the sites of the chemical sensitization reaction to control and centralize the development start site. The CR compound according to the present invention may be adsorbed on silver halide formed in at least 85%, preferably at least 90 mol% of the silver halide grains. What is particularly important is that, as described above, the chemical sensitizer used for chemical sensitization has an adsorptivity on the surface of silver halide grains, a reaction activity and a relative adsorptivity with a CR-compound. It has been found that there is a particularly suitable chemical sensitizer depending on the crystal habit, halogen composition and the like. Generally, conventionally known gold sensitization, noble metal sensitization, sulfur sensitization, reduction sensitization, etc. can be used alone or in combination.

As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, U.S. Pat. Nos. 2,448,060 and 3,320,069) or a sensitization method using a metal such as iridium, platinum, rhodium, palladium (for example, U.S. Pat. 2,566,2
No. 45, No. 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264), a selenium sensitization method using a selenium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamine or the like ( US Patent No.
2,487,850, 2,518,698, and 2,521,925), or a combination of two or more of these.

In particular, the silver halide grains of the present invention are preferably gold sensitized or a combination of gold sensitization and sulfur sensitization or reduction sensitization, and gold plus sulfur sensitization is particularly preferred.

The use amount of the gold sensitizer is preferably at least 5 × 10 ^-6 mol, more preferably at least 1.5 × 10 ^-5 mol, per mol of silver halide. The amount of the sulfur sensitizer that can be used together with this is
The optimum amount can be selected according to conditions such as the particle size, the temperature of chemical sensitization, pAg, and pH. It is used in an amount of 10 ^-7 to 10 ^-3 mol, preferably 5 × 10 ^-7 to 10 ^-4 mol, and more preferably 5 × 10 ^-7 to 10 ^-5 mol, per mol of silver halide.

Preferred gold sensitizers are chloroauric acid and its salts, and it is also useful to use thiocyanate in combination to enhance gold sensitization as described in James, p. 155.

Examples of the sulfur gold enhancer that can be used in combination in the present invention include thioureas such as sodium thiosulfur and tetramethylthiourea, and rhodanine compounds.

A feature of the present invention is that the chemical sensitization with more gold sensitizer than is usually used increases the sensitivity / fogging ratio.

The silver halide emulsion of the present invention may be optionally treated with an oxidizing agent after grain formation. This method is described in JP-A-60-136736 (corresponding European Patent No. 144990A2).

The CR-compound represented by the general formula [I], [II] or [III] of the present invention also serves as a spectral sensitizing dye, but if necessary, can be spectrally sensitized by adding a sensitizing dye after chemical sensitization.

The sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
An oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, , Indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

For example, Research Disclosure, Item 17643, page 23 IV
The compound described on page (December 1978) or the compound described in the cited document can be used.

The silver halide emulsion of the present invention can further reduce the fog of the light-sensitive material by adding a compound having a mercapto group, improve raw storage stability, and improve the temporal stability of the emulsion coating solution before the production of the light-sensitive material. Can be improved.

Usually, tetrazaindenes are commonly used for these purposes, and very small amounts of mercapto-containing compounds can be used for these purposes in limited amounts. If it is less than the optimum range, it becomes invalid. Unexpectedly, the emulsion of the present invention preferably contains a mercapto compound, which is considered to have a strong inhibitory effect, particularly a water-soluble mercapto compound, for the above purpose, and has less adverse effects such as desensitization and development suppression.

In the color light-sensitive material using the silver halide emulsion according to the present invention, a color coupler represented by the following general formulas [IX] to [XIII] is preferably used.

(Wherein P is a substituted or unsubstituted t-butyl group, phenyl group or anilino group, R ₂₁ , R ₂₄ and R ₂₅ are an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic amino group, Represents an aromatic amino group or a heterocyclic amino group, R ₂₂ represents an aliphatic group, R ₂₃ and R ₂₆ each represent a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group; it can be coupled to ring closure ₂₂ and R _23.

R ₂₇ and R _{29 each} represent a substituted or unsubstituted phenyl group; R ₂₈ represents a hydrogen atom, an aliphatic or aromatic acyl group,
Represents an aliphatic or aromatic sulfonyl group, R ₃₀ represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, and Za and Zb represent methine, substituted methine, or −N- Y ₁ , Y ₂ and Y ₄ represent a halogen atom or a group capable of leaving during a coupling reaction with an oxidant with a developing agent (hereinafter abbreviated as a leaving group), and Y ₃ represents a hydrogen atom or a leaving atom Y ₅ represents a leaving group, and in the general formulas [IX] and [X], R ₂₂ and R ₂₃ and R ₂₅ and R ₂₆ each form a 5, 6 or 7-membered ring; Is also good.

R ₂₁ , R ₂₂ , R ₂₃ or Y ₁ ; R ₂₄ , R ₂₅ , R ₂₆ or Y ₂ ; R
₂₇ , R ₂₈ , R ₂₉ or Y ₃ ; R ₃₀ , Za, Zb or Y ₄ ; Q or Y ₅ may form a dimer or higher multimer.

The general formulas (IX), (X), (XI), (XII) and (X
III], R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R
_{29, R 30, Za, Zb} , Q 1, Y 1, Y 2, for Y ₃ and details of Y _4, Japanese Patent Application Sho 61-175233 (1986 July 25 available from Fuji Photo Film Co., filed ) The general formulas (I), (II), (III) described in pages 17 to 34 of the specification of the patent application.
It is the same as that of (IV) and (V).

Specific examples of these color couplers include (C-1) to (C-40), (M-1) described on pages 36 to 78 of Japanese Patent Application No. 61-175233. ) ~ (M ~ 42),
(Y-1) to (Y-46) can be mentioned, and the following compounds are more preferable.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
The amount is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In a light-sensitive material using a color coupler represented by the general formula [IX], [X], [XI], [XII] or [XIII], the preferable silver halide coating amount is determined by using a reflective support. a ^{1.5g / m 2 ~0.1g / m 2} , the case of using the transparent support is a ^{7g / m 2 ~0.2g / m 2} .

As the coupler used in the present invention, it is preferable to use a so-called high-speed coupler having high coupling reactivity.

The coupling reactivity of the coupler is determined by mixing each of the two types of couplers M and N, which give different dyes which can be clearly separated from each other, and adding the resulting mixture to an emulsion to form a color image. It can be determined as a relative value by measuring the amount of the dye.

Maximum density (DM) max. Of coupler M, density D in the middle stage
The color development of M and each (DN) m for coupler N
ax., DN, the reaction activity ratio of both couplers
RM / RN is represented by the following equation.

In other words, the emulsion containing the mixed coupler is exposed to various stages, and several sets of DM and DN obtained by color development are subjected to two axes orthogonal to each other. The coupling activity ratio RM / RN is determined from the slope of the straight line obtained by plotting.

Here, when the value of RM / RN is determined for various couplers as described above using a fixed coupler N, the coupling reactivity is relatively determined. The above coupler N may be determined, for example, by using the following coupler.

Magenta coupler, against yellow coupler As the high-speed reaction coupler used in the present invention, the RM / RN value obtained using the above-mentioned coupler N has a value of 1.5 or more for a cyan coupler, 2.5 or more for a magenta coupler, and a value of more than 1 for a yellow coupler. Are each preferred.

Hereinafter, specific examples of preferred high-speed reaction couplers to be used in the present invention are shown, but the present invention is not limited thereto.

Example of cyan coupler Example of magenta coupler Example of yellow coupler In the present invention, such a high-speed reaction coupler is preferably added to at least the unit emulsion layer having the highest sensitivity among the respective color-sensitive layers. Although there is no particular limitation on the amount of the cyan coupler, the cyan fast reaction coupler per mol of silver is 0.005 to 0.5.
1, the range of the magenta fast reaction coupler 0.005 to 0.1 and the yellow fast reaction coupler 0.005 to 0.1 are preferred.

Also, in the present invention, the dyes defined in paragraphs 1 and 3 to 8 of U.S. Pat. No. 4,420,556 and JP-A No. 59-191036 are suitable for a diffusion-resistant coupler having a moderate diffusibility. It is possible to improve the sensitivity and the granularity by improving the covering power by using. These couplers are disclosed in the above patent and
No. 1938, No. 57-3934, No. 53-105226, U.S. Pat.
According to the method described in JP-A-264,723 and the like, it can be easily synthesized.

Specific examples include those described in Japanese Patent Application No. 61-201756, pages 54 to 58.

Functional coupler In the present invention, various functional couplers are used. DIR-couplers represented by the following general formulas [XIX] to [XX] and hydroquinone derivative releasing couplers are used.

In particular, it is particularly advantageous in improving the graininess and sharpness of an image, and the effects of color correction between layers, softening of gradation, and the like are strongly exhibited.

In the present invention, particularly, among DIR compounds, the following general formula (XIX)
Or selected from the group of compounds represented by [XX]
Preferably, a DIR compound is used.

In the formula, A is a color coupler residue or a coupler residue which reacts with an oxidized form of the active ingredient and does not form a coloring dye, for example, U.S. Patent Nos. 3632345 and 3959893;
And the residues described in JP-A-52-161237.

The following can be used as the color coupler residue. As the yellow color coupler residue represented by A, there are piperoyl acetoanilide type, benzoylacetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, benzothiazolyl acetate Type, benzoxazolylacetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolyl acetate type coupler residue, or derived from heterocyclic substituted acetamide or heterocyclic substituted acetate contained in U.S. Pat.No. 3,841,880. Coupler residue or U.S. Pat.
770,446, UK Patent 1,459,171, West German Patent (OLS)
No. 2,503,099, coupler residues derived from acylacetamides described in JP-A-50-139,738 or Research Disclosure 15737, or U.S. Pat.
The heterocyclic-substituted coupler residues described in No. 574 are preferred.

The magenta color residue represented by A is 5
-Oxo-2-pyrazolin nucleus, pyrazolo- [1,5-a]
A benzimidazole nucleus, a cyanoacetophenone type coupler residue or a coupler residue having a pyrazolotriazole nucleus is preferred.

The cyan color coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Further, after the coupler residue represented by A couples with the oxidized form of the developing agent to release the development inhibitor, substantially no dye may be formed. Nos. 4,052,213 and 4,082,213 disclose coupler residues of this type represented by A.
No. 8,491, No. 3,632,345, No. 3,958,993 or No.
3,961,959.

A means that it reacts with the oxidized form of the color developing agent Or Is a coupler residue.

L ₁ is a group that cleaves the residue bonded to L ₁ after cleavage from A.
Represents 0 or 1. Examples of the linking group represented by L ₁ include the following.

—OCH ₂ — (the linking group described in US Pat. No. 4,146,396) —SCH ₂ ——OCO— (the linking group described in West German Patent Publication No. 2626315) Linking groups shown below are intended to be encompassed by L ₁ in the present invention in which reacts with cleavage further oxidized developing agent from A to release a development inhibitor.

(Linking group described in JP-A-61-233741) R ₃₁ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, an ureido Group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, cycloalkyl group, alkane sulfonyl group, arylsulfonyl group or acyl group, R ₃₂ is a hydrogen atom, Represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group.

 V represents a 5- or 6-membered ring-forming atom.

p and q each represent 1 or 2, and when they are 2, they may be the same or different.

Z ₄ represents a divalent linking group such as an unsubstituted or substituted arylene, straight-chain or branched alkylene such as a heterocyclic ring such as diazolyl, triazolyl, tetrazolyl, thiadiazolyl, and oxazolyl groups.

Z ₅ represents a divalent heterocyclic residue.

L ₂ represents a linking group.

X and Y represent a hydrogen atom, an alkyl group or an alkenyl group, an aryl group or a heterocyclic residue.

 b represents 0, 1 or 2, and c represents 0 or 1.

In the light-sensitive material of the present invention, the coating amount of the DIR compound or the hydroquinone derivative-releasing coupler is 5 × 10 ⁻⁴ mol or less, preferably 1 × 10 ⁻⁴ mol or less per 1.0 g of the silver-sensitive coating amount of the photosensitive silver halide. When the silver iodide content of the photosensitive silver halide is 2 mol% or less, preferably 1 mol% or less, it is advantageous to prevent desilvering inhibition even when bleach-fixing for about 3 minutes or less. It is.

In order to improve sharpness, an unsharp mask method is often used in addition to using the DIR coupler.
For example, French Patent No. 2260124, JP-A-61-201246
And No. 61-169843.

In the present invention, other functional couplers such as the following, colored couplers, chromogenic diffuser couplers, polymer couplers, photographically useful residue-releasing couplers,
Etc. can be used.

In order to correct unnecessary absorption of various coloring elements, it is preferable to perform masking by using a colored coupler in combination with a color photographic material for photography. U.S. Pat.No. 4,163,670 and Japanese Patent Publication No. 5
7-39413 or the like, or magenta-colored cyan couplers, cyan-colored yellow couplers, or cyan-colored magenta couplers described in U.S. Pat. And the like are typical examples. Other colored couplers are RD17643, VII-G
It is described in the section.

U.S. Pat.Nos. 4,553,477, 4,555,478, 4,55
Masking agents having a leaving group with a ligand capable of forming a chelate dye described in 7,998 and 4,568,633 are also preferably used.

Granularity can be improved by using a coupler having a moderately diffusible color forming element. Such couplers are disclosed in U.S. Pat.Nos. 4,366,237 and 2,125,570.
No. 1 contains specific examples of magenta couplers, and EP 96,5
No. 70 and West German Application Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

Dye-forming couplers and the aforementioned special colors may form polymers of dimer or higher. Typical examples of polymerized dye-forming colors are U.S. Pat.
Nos. 4,080,211 and 4,455,366.
Specific examples of polymerized magenta couplers are described in British Patent No. 2,
No. 102,173, U.S. Pat.Nos. 4,367,282 and 3,926,43
It is described in No. 6. Further, as polymer couplers imparted with water solubility, JP-A-60-218646, JP-A-58-28744,
The couplers described in U.S. Pat. Nos. 4,207,109 and 4,215,195 are also preferably used.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the aforementioned RD17643, VII-F are useful.

In the light-sensitive material of the present invention, a coupler which releases an image-like nucleating agent or development accelerator or a precursor thereof during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. Couplers which release a nucleating agent or the like which has an adsorbing effect on silver halide are particularly preferred, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

Other couplers that can be used in the light-sensitive material of the present invention include competing couplers (for example, US Pat. No. 4,130,
427), multi-equivalent couplers (for example, U.S. Pat. Nos. 4,283,472, 4,338,393,
Couplers described in, for example, JP 310,618), DIR redox compound releasing couplers (e.g., couplers described in JP-A-60-185950), and dye releasing couplers which recolor after release (e.g., described in EP-A-173,302). Certain couplers) and the like.

Further, JP-A-61-201247, Research Disclosure No. 11449 (October 1973) and No. 24241 (19
The use of a bleaching accelerator releasing coupler described in June 1984) is particularly preferable because the desilvering step is accelerated.

Hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, and the like may be contained as an inhibitor or an anti-fading agent.

Other Materials As oxidized scavengers of the developing agent that can be used in the present invention, in addition to commonly known hydroquinone derivatives, U.S. Pat.No. 4,474,874, JP-A-59-5247, U.S. Pat.
Compounds described in U.S. Pat. Nos. 4,584,264 and 4,447,523 are preferred.

In the light-sensitive material of the present invention, a known anti-fading agent can be used. Examples of the organic fading inhibitor include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzene Kind,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 give good results in preventing deterioration of the yellow dye image due to heat, humidity and light. Further, in order to prevent deterioration of the magenta dye image, particularly deterioration due to light, spiroindanes described in JP-A-56-159644, and haloloquinone diethers or monoethers described in JP-A-55-89835 are used. Substituted chromans give favorable results.

The image stabilizer described in JP-A-59-125732 is particularly advantageous for stabilizing a formed magenta image using a pyrazolotriazole type magenta coupler.

In order to improve the storage stability of the cyan image, particularly the light fastness, it is preferable to use a benzotriazole-based ultraviolet absorber in combination. This UV absorber may be co-emulsified with a cyan coupler.

The coating amount of the ultraviolet absorber may be sufficient to provide light stability to the cyan dye image, but if used in an excessively large amount, unexposed portions (white background) of the color photographic light-sensitive material may cause yellowing. Usually preferably 1 × 10 ⁻⁴ mol / m ²
~ 2 × 10 ^-3 mol / m ² , especially 5 × 10 ^-4 mol / m ² 〜1.5 × 10 ^-3
It is set in the range of mol / m ² .

In addition to the above-mentioned additives, the photosensitive material of the present invention may further contain various stabilizers, antifouling agents, developing agents or precursors thereof, development accelerators or precursors thereof, lubricants, dye mordants, matting agents, charging agents. Inhibitors, plasticizers, or other various additives useful for photographic materials may be added. Typical examples of these additives are Research Disclosure
17643 (December 1978) and 18716 (November 1979).

The couplers and related materials used in the present invention can be introduced into the photosensitive material by various known dispersion methods, for example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. A typical example can be mentioned. In the oil-in-water dispersion method, the boiling point is 17
After dissolving in a single liquid or a mixture of both high-boiling organic solvents having a temperature of 5 ° C. or higher and so-called auxiliary solvents having a low boiling point, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling organic solvents are described in U.S. Pat. No. 2,322,027 and the like. Dispersion may involve phase inversion, and if necessary, may be used for coating after removing or reducing the auxiliary solvent by distillation, noodle washing, or ultrafiltration.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, gelatin and other macromolecules and graft polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates and the like; sugar derivatives such as sodium alginate and starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used.

As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Phot. Japan. No. 16, page 30 (196
Oxygen-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, a coating aid, antistatic, improvement of sliding property, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (eg development acceleration, high contrast, sensitization) Various known surfactants may be included for various purposes.

Nonionic surfactants such as, for example, saponins, polyoxyethylene compounds, glycidol derivatives (eg, alkenyl succinic acid polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and urethanes or ethers; Triterpenoid saponins, alkyl carboxylate, alkyl benzene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines,
Anionic surfactants such as sulfosuccinates and sulfoalkylpolyoxyethylene alkylphenyl ethers; amino acids, aminoalkylsulfonic acids,
Aminoalkyl sulfates or phosphates, alkylbetaines, amine imides, amine oxides and other double-sided surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, and heterocyclic quaternary compounds such as pyridinium and imidazolium Cationic surfactants such as quaternary ammonium salts and aliphatic or heterocyclic containing phosphonium or sulfonium salts can be used. For the purpose of antistatic, a fluorinated surfactant is preferably used.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, glycidyl (meth) acrylate, etc., alone or in combination,
Alternatively, a polymer having a combination of these and acrylic acid, methacrylic acid, or the like as a monomer component can be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts, aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds, active vinyl compounds (1,3,5-triacryloyl-hexacido-s-triazine, bis (vinylsulfonyl) methyl ether, etc.), activity Halogen compounds (2,4
-Dichloro-6-hydroxy-s-triazine, etc.),
Mucohalogenic acid and the like can be used alone or in combination.

The silver halide emulsion according to the present invention can be used as described in Research Disclosure No. 15162, No. 16345, No. 17643, No. 18716.

The silver halide photographic emulsion according to the present invention can be used for both color light-sensitive materials and black-and-white light-sensitive materials. When used for a high-sensitivity photosensitive material, particularly for a photographic photosensitive material, its effect is utilized.

The color light-sensitive material comprises a support, a red-sensitive layer containing a cyan coupler, a green-sensitive layer containing a magenta coupler, a blue-sensitive layer containing a yellow coupler, a filter layer, an antihalation layer, and an intermediate layer. , A protective layer and the like.

Further, for example, a functional photosensitive layer or a layer structure as described in JP-B-55-34932 or JP-A-62-25287 is preferably used. By appropriately combining the type of coupler and the spectral sensitivity distribution, it can be used for color print photographic materials, other false color photographic materials, color recording materials using digital scanning exposure, and Japanese Patent Application Laid-Open Nos. It can be used in a layer constitution described in, for example, No. 127437 or No. 62-37797.

Black-and-white photosensitive materials are useful for black-and-white photographic paper, photographic photosensitive materials, suppression photographic materials and the like. One or more photosensitive layers may be formed on a support as described in, for example, Japanese Patent Application No. 61-202549. And a protective layer, an intermediate layer, an antihalation layer, a filter layer, and the like.

The light-sensitive material using the silver halide photographic emulsion of the present invention,
Various exposure means used for other photosensitive materials can be used. However, the photosensitive material of the present invention can provide excellent finish quality with a small degree of variation due to exposure conditions with respect to the progress of development and the obtained gradation, as compared with the conventional photosensitive material.

Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-embedded lamps, mercury lamps, fluorescent lamps, and strobe or metal burning flash bulbs are common. Gas that emits light in the wavelength range from ultraviolet to infrared
Dye solution or semiconductor laser, light emitting diode,
It can be used for a plasma light source or a recording light source. In addition, a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or a micro-shutter array using lanthanum-doped lead zirconate titanate (PLZT) or the like has a linear or Exposure means combining a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The silver halide photographic emulsion of the present invention is a photographic emulsion in which not only development start sites and the number thereof are controlled, but also grains having uniform development start times. Therefore, by using photographic emulsions having different sensitivities, for example, by forming one image forming layer into a multi-layer structure such as two to four green-sensitive layers of a color negative light-sensitive material, silver It is possible to improve the use efficiency of silver halide by reducing the amount, and to improve the graininess and image sharpness.

Next, a preferred method for developing a color light-sensitive material or a black-and-white light-sensitive material using the silver halide photographic emulsion of the present invention will be described.

The color developer used in the development of the photosensitive material of the present invention is
This is an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the aromatic primary amine-based color developing agent, aminophenol-based compounds are also useful, but p-phenylenediamine-based compounds are usually suitable, such as 3-methyl-4-amino-N, N -Diethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and sulfates thereof,
Hydrochloride, phosphate, p-toluenesulfonate, tetraphenylborate, p- (t-octyl) benzenesulfonate and the like.

From the viewpoint of simplifying and speeding up the processing aimed at by the present invention, the photosensitive material of the present invention preferably has a particularly high developing speed and a small fluctuation in developing activity even in low replenishment processing. A developing agent represented by the general formula [XX], having -methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline as a typical example, is preferable.

In the formula, R ₆₁ represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms) or R ₆₂ , and R ₆₂ represents-(R ₆₄ O) m- (R
₆₅ O) represents the n-R _66, R ₆₄ and R ₆₅ may be the same or different and an alkylene group (preferably having a carbon number of 1
To 4), wherein m and n are each 0 or an integer of 1 to 4 and are not simultaneously 0. R ₆₆ represents a hydrogen atom, an aryl group (preferably having 6 to 8 carbon atoms) or an alkyl group (preferably having 1 to 6 carbon atoms). R ₆₃ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylsulfonamide group, an acylamide group, or an amino group.

The number of carbon atoms of choice in R ₆₃ is preferably 1-4.

These color developing agents are generally used per color developing solution.
1 g to 30 g, preferably 2 g to 20 g, particularly preferably 3 g to 10 g
Used in the range.

The color developing agents including the compound represented by the general formula [XX] are often used alone, but if necessary, they can be used in combination with one another of the same general formula or with different types of main agents. -Methyl-4-amino-N-
A combination of ethyl-N-β-hydroxyethylaniline and 3-ethyl-4-amino-N-β-methanesulfonamidoethylaniline or 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline And 3-methyl-
Combinations with 4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline can be mentioned.

The color developing solution is a pH buffer such as an alkali metal carbonate, borate or phosphate; a development inhibitor such as chloride, bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds; Antifoggants; hydroxylamine, diethylhydroxylamine, triethanolamine, West German Patent Application (OLS) No. 262
No. 2950, compounds described in Japanese Patent Application No. 61-265149, preservatives such as sulfites or bisulfites; or oxidized forms of color developing agents described in Japanese Patent Application No. 61-259799. It is preferable to use a reconstituting agent or a capturing agent for the same. Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diol; competitive couplers; Auxiliary developing agents such as 3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexadiaminetetraacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, Aminopolycarboxylic acid represented by triethylenetetramine hexaacetic acid and compounds described in JP-A-58-195845, 1-hydroxyethylidene-1,1'-diphosphonic acid, Research Disclosure 18170 (May 1979) Organic phosphonic acid, aminotris (meth Lenphosphonic acid) ethylenediamine
Aminophosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid; JP-A-52-102726; JP-A-53-42730;
4-121127, 55-4024, 55-4025, 55-126
Chelating agents such as phosphonocarboxylic acids described in JP-A Nos. 241, 55-65955, 55-65956, and Research Disclosure No. 18710 (May, 1979) can be contained.

The pH of the color developing solution is usually in the range of 8 to 13, preferably 9 to 12, and particularly preferably 9.5 to 11.5. The temperature in the treatment is in the range of 25 to 50 ° C, but is preferably in the range of 30 to 50 ° C, particularly preferably 35 to 45 ° C for speeding up.

In processing the light-sensitive material of the present invention, the color developing solution is 1 × 10
It preferably contains ^-3 mol / .about.2.times.10.sup.- ¹ mol / water-soluble chloride, particularly preferably 5.times.10.sup.- ³ mol / .about.5.times.10.sup.- ² mol /. As the water-soluble chloride, potassium chloride and sodium chloride are preferably used.

When the light-sensitive material of the present invention is processed continuously, the color developing solution can be continuously used while being replenished. The replenishment amount is preferably 1 to 10 ml per 100 cm ² of the light-sensitive material of the present invention. 3 × 10 ^-3 mol / ~ 3 × to prevent fog
It is also preferable to contain 10 ^-2 mol / water-soluble bromide, and it is preferable to use potassium bromide or sodium bromide as such a water-soluble bromide.

In the developing method of the present invention, it is preferable to use a color developing solution substantially free of iodide ions. Here, “substantially not contained” means an iodide ion content of 1.0 mg / or less.

In the present invention, the color developing solution preferably does not contain a sulfite as long as its oxidation in the air can be prevented and its preservation can be maintained. 4g per liter as sulfurous anhydride
The density is preferably not more than 2 g, more preferably not more than 1 g, so that the density of the coloring dye can be improved.

The processing time with these color developing solutions is from 10 seconds to 3 minutes, preferably from 10 seconds to 2 minutes, particularly preferably from 20 seconds to 2 minutes.
1 minute and 30 seconds.

The light-sensitive material of the present invention is subjected to a color developing solution and a desilvering process. The desilvering treatment is performed by a method using two baths of a bleaching solution and a fixing solution.
A method using two baths of a bleaching solution and a bleach-fixing solution described in JP-A-61-75352; a method using two baths of a fixing solution and a bleach-fixing solution described in JP-A-61-51143; Can be carried out by any of the methods described above. However,
For the purpose of simplification and speed, the light-sensitive material of the present invention is preferably processed with a bleach-fix solution in a single tank or a plurality of tanks.

Bleaching agents used in bleaching solutions and bleach-fixing solutions include ferric salts, persulfates, dichromates, bromates, red blood salts,
Aminopolycarboxylic acid ferric complex salts and the like,
For the photosensitive material of the present invention, it is preferable to use a ferric aminopolycarboxylic acid complex salt.

Examples of preferred aminopolycarboxylic acid ferric complex salts are described below.

(1) Ferric complex of ethylenediaminetetraacetic acid (2) Ferric complex of diethylenetriaminepentaacetic acid (3) Ferric complex of cyclohexanediaminetetraacetic acid (4) Ferric complex of iminodiacetic acid (5) Ferric methyl iminodiacetate Complex salts (6) Ferric complex salt of 1,3-diaminopropanetetraacetic acid (7) Ferric complex salt of glycol ether diaminetetraacetic acid The above ferric complex salts of aminopolycarboxylic acid are sodium salt, potassium salt and ammonium salt thereof. Is usually used, and it is particularly preferable to use it as an ammonium salt.

The concentration of the aminopolycarboxylic acid ferric complex salt in the bleaching solution and the bleach-fixing solution is 0.05 to 1 mol /, preferably 0.1 to 1 mol /, particularly preferably 0.1 to 0.5 mol /.
It is.

In the bleaching solution or the bleach-fixing solution, a bleaching accelerator can be used if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent No.
No. 0,812, 2,059,988, JP-A-53-32736, 53-53
No. 7831, No. 37418, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53-104232, No. 53
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July 1978), bromides and chlorides (for example, potassium chloride) , Sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide). Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate,
One or more inorganic acids, organic acids and alkali metal or ammonium salts thereof having a pH buffering capacity such as phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and corrosion inhibitors such as ammonium nitrate and guanidine Etc. can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, that is, ammonium thiosulfate such as sodium thiosulfate and ammonium thiosulfate; thiocyanate such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid And thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide solubilizers such as thioureas. Compounds having these; described in JP-A-50-140129. Thiazolidine derivatives such as JP-B-45-8506, JP-A-52-20832,
Nos. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent 1,127,715, iodides described in JP-A-58-16235; West German Patents 966,410, and polyethylene described in 2,748,430. Oxides; polyamine compounds described in JP-B No. 45-836;
No. 49-59644, No. 53-94927, No. 54-35727,
Compounds described in JP-A-55-26506 and JP-A-58-163940 and iodine and bromine ions can be exemplified. Among them, a compound having a mercapto group or a disulfide group has a large accelerated curing property, and is particularly preferable in US Pat. No. 3,893,858.
And compounds described in West German Patent No. 1,290,812 and JP-A-53-95630.

In addition, a bromide (for example, potassium bromide or sodium bromide) can be used alone or as a mixture of two or more kinds in the bleaching solution or the bleach-fixing solution.
The use of thiosulfates, especially ammonium thiosulfates, is preferred.

The amount of the fixing agent per one is preferably 0.3 to 2 mol, particularly preferably 0.8 to 1.5 mol.

The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering can be carried out and stain tends to occur. The pH of the bleaching solution is from 4 to 7, preferably from 4.5 to 6.5. At pH 4 or lower, leuco-formation of the cyan dye occurs, and at pH 7 or higher, desilvering delay occurs.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

The bleach-fixing solution and the fixing solution include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. (E.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of 0.02 to 0.50 mol / mol, more preferably 0.04 to 0.40 mol / mol, in terms of sulfite ion.
It is.

As a preservative, sulfite is generally added,
In addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like can be used.

The temperature of the desilvering treatment is preferably high as long as excessive softening of the gelatin film and deterioration of the processing solution do not pose a problem. A specific temperature range that can usually be selected is 30-50 ° C. Although the desilvering time is slightly different depending on the desilvering method employed, it is usually 4 minutes or less, preferably
30 seconds to 3 minutes.

The photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing processing after desilvering processing such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing process can vary widely depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set. Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Television
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multi-current system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, the amount can be 0.5 L-1 L or less per 1 m ^{2 of the} photosensitive material. However, an increase in the residence time of water in the tank causes a problem that bacteria proliferate and the generated suspended matter adheres to the photosensitive material. In the processing of the color light-sensitive material of the present invention,
As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. In addition, JP
No.-8542, isothiazolone compounds and thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in JP-A 61-120145, benzotriazole described in JP-A-61-267611, and others Fungicides described in Hiroshi Horiguchi, "The chemistry of antibacterial and antifungal agents", edited by the Japan Society of Sanitary Engineers, "Sterilization, sterilization, and antifungal technology of microorganisms", edited by the Japanese Society of Antibacterial and Antifungal Products, "Encyclopedia of Antifungal and Antifungal Agents" Can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, and the like, but are generally in the range of 15 to 45 ° C for 20 seconds to 10 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 5 minutes. Selected.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Nos. 8543, 58-14834, 59-284343, 60-220345, 6
0-238832, 60-239784, 60-239749, 61-4054
And known methods described in JP-A-61-118749 can be used.

In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, and a bismuth compound.

The liquid used in the washing and / or stabilizing step can be used in the previous step. An example of this is to reduce the amount of waste liquid by replenishing the bleach-fix bath with the over-flush of the washing water reduced by the multi-stage countercurrent method into the bleach-fix bath preceding the bath.

When a large amount of photosensitive material is processed by the development processing method of the present invention, it is desirable to perform continuous processing. In the case of disc-shaped film, etc., the exposed photosensitive material can be placed in a certain bath, and color development, bleach-fixing, washing and stabilization can be performed sequentially. A system in which photosensitive materials are sequentially conveyed into these processing baths is preferred. Guide film method for transport method,
Roller conveyance, rack guidance system, etc. are available.

When continuously developing a long photosensitive material, replenish the processing bath with a processing solution and replenish the consumption components based on the processing.
The removal of the adverse effects associated with the accumulation of the processing solution of the eluted components from the photosensitive material is performed. It is also desirable to correct the composition change due to the air oxidation of the developer. It has been devised to reduce the amount of waste liquid by reducing the amount of replenisher. In particular, the use of the overflow solution of the washing / stabilizing solution in the previous step is as described above, and the overflow solution of the developer can also be used in the bleach-fix bath.

The development processing time of the present invention can be about 1 to 5 minutes from the start of development to the end of drying, preferably 1 to 3.5 minutes, more preferably 120 seconds or less.

For the photographic processing of the black-and-white light-sensitive material produced by applying the present invention, any of known methods can be used. Known treatment liquids can be used. Processing temperature is normal
The temperature is selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

For details, see Research Disclosure, Volume 176, No.
Developing can be performed by the method described in 17643, pp. 28-29, and 187, No. 18716, page 651, left column, right column.

Known developing agents such as dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and aminophenols (for example, N-methyl-p-aminophenol) are used in the black-and-white developer. It can be used alone or in combination.

(Effect of the Invention) By using the silver halide photographic emulsion (CDG, EDG) according to the present invention, the following black-and-white photographic materials, color reversal for photography, color negative photographic materials, color print photographic materials and full-color recording materials can be obtained. be able to.

(1) A photosensitive material having high sensitivity and excellent raw storability, latent image stability and reciprocity failure characteristics (2) Exposure conditions (temperature, time, etc.), development conditions (temperature,
(3) Photosensitive material with stable finish quality against fluctuations of time, density, etc. (3) Photosensitive material with improved simplification of development processing and improved processing stability, especially black-and-white photosensitive material that can be developed in less than 45 seconds Color negative photosensitive material capable of color development and desilvering for 9 minutes or less, preferably 4 minutes or less. (4) High sensitivity can be obtained with a low silver iodide type or high silver chloride type silver halide emulsion and a specific coupler (especially a high speed reaction) Coupler), DIR-coupler (or compound) or CR-compound to select a color printing material and a color / negative material.

(Preferred embodiments of the silver halide light-sensitive material of the present invention) (1) At least one blue-sensitive layer on a support,
In a color light-sensitive material provided with a green-sensitive layer and a red-sensitive layer, the silver halide emulsion of the present invention was used, and further represented by general formulas (IX), (X), (XI), (XII) and (XIII). A color photographic material using a color coupler selected from the compounds described above, especially a highly active color coupler; (2) a color photographic material further selected from the compounds represented by the general formulas [XIX] and [XX] in the above (1) Color negative photosensitive material using functional coupler (3) In the above (1) or (2), desilvering from color development using the silver halide emulsion according to the present invention having an average silver iodide content of 4 mol% or less. Color negative light-sensitive material capable of performing color development within 9 minutes, preferably 4 minutes, of the process (excluding drying) Preferred embodiments of the silver halide emulsion of the present invention are as follows: (1) Silver halide photographic emulsion 2. The silver halide photographic emulsion according to claim 1, wherein the silver halide crystals present in (a) are substantially normal crystal grains having a (111) plane, and are of a vertex development type and / or a ridge development type. CR- selected from the group of compounds and nucleic acids represented by the general formulas [I] to [V] described above.
A vertex-developing type and / or a ridge-development type silver halide emulsion prepared by adding the compound during or before the chemical sensitization step. (3) The average silver iodide content is 4 mol% or less. Silver halide (silver bromide, silver chlorobromide, or silver chloride), and (111)
Claims (1) and (2), wherein the silver halide photographic emulsion comprises normal crystal grains having a plane. (4) A silver halide having an average silver chloride content of at least 70 mol%, and (111) The silver halide photographic emulsion according to the claims, comprising substantially normal crystal grains having planes. (6) Compounds represented by the general formulas [I] to [V] described in the text on the surface of the (111) plane grain base; After the CR compound selected from the nucleic acid compounds is adsorbed, silver halide of 15 mol% or less of the total silver halide is added for ripening or halogen conversion. Or a silver halide photographic emulsion according to the present invention, characterized in that it contains CDG and / or EDG obtained by chemical sensitization after adsorption. Or the compound represented by [V]. (8) 15 mol% or less of the total silver halide after the CR compound is adsorbed on the surface of the (111) face grain matrix. The emulsion according to the claims, characterized in that the emulsion contains CDG and / or EDG obtained by newly growing silver halide by adding an amount of CDG and / or chemically sensitized. Will be described. However, it is not limited to this.

Example 1 Preparation of Emulsions F and G Ammonia was added while vigorously stirring an aqueous gelatin solution kept at 60 ° C., and then an aqueous silver nitrate solution and an aqueous potassium bromide solution were added simultaneously. During the addition, pAg
It was kept at 8.9.

The resulting emulsion was a monodispersed, octahedral pure silver bromide emulsion having an average grain size of about 0.85μ.

Then, after washing with water and desalting by a flocculation method according to a conventional method, pH and pAg were adjusted to 6.5 and 8.7, respectively.

This emulsion was divided into two parts. One of the emulsions was heated to 60 ° C., and then sodium thiosulfate was added per mole of silver halide.
0 mg, 3.6 mg of chloroauric acid and 80 mg of potassium thiocyanate were sequentially added and aged for 40 minutes.
The temperature was reduced to 0 ° C. (Emulsion F) The other emulsion was heated to 60 ° C., and then 250 mg of ribonucleic acid was added per mole of silver halide, 8.0 mg of sodium thiosulfate was added, and after 35 minutes, 3.6 mg of chloroauric acid was added. After 80 mg of potassium thiocyanate was added and the mixture was aged for 5 minutes, 100 mg of ribonucleic acid was added to bring the temperature to 40 ° C.

(Emulsion G) These emulsion stabilizers (4-hydroxy-6-methyl- (1,3,3a, 7)-
Tetrazaindene), a coating aid (sodium dodecylbenzenesulfonate), and a gelatin hardener (2,4-dichloro-6-hydroxy-S-triazine soda) and a surface protective layer on a cellulose acetate film support. At the same time, samples were applied by an extrusion method to obtain samples 6 and 7.

These samples 6 and 7 were exposed to light for 1/100 second through a light wedge, developed with Kodak prescription D-19 developer at 20 ° C. for 10 minutes, then stopped and fixed.

 Table 1 shows these results.

The relative sensitivity is represented by the reciprocal of the exposure required to obtain an optical density of fog value +0.5, and the value of sample 6 is set to 100.

Observation of the development centers of Samples 6 and 7 was performed as follows.

It is 1.5 in Δloge from the exposure amount that gives the density of fog value +0.5
The high exposure was evenly applied to the sample. Next, after developing with a diluted developer having the following composition at 20 ° C. for 10 minutes, the silver halide emulsion was removed from the support using a pronase enzyme. Thereafter, a small amount of this emulsion was put on a micromesh for an electron microscope, carbon was vapor-deposited in a vacuum, and immersed and fixed in a fixing solution to prepare a carbon precursor, which was observed with an electron microscope.

Developer for observation of development center Electron micrographs of silver halide grains in the emulsions of Samples 6 and 7 are shown in FIG. 1 and FIG.

As is clear from the photograph, compared to Sample 1, Sample 7 clearly has developed silver (black dots) formed at the apexes of the octahedral grains, and Sample 7 also has excellent photographic performance, as is clear from Table 1. It was.

Example 2 Preparation of Emulsion A silver halide emulsion was prepared as follows.

Solution 1 Bone gelatin 30 g NaCl 3.8 g H ₂ O 1000 cc NH ₄ NO _{3 3} g Solution 2 AgNO ₃ 15 g NH ₄ NO ₃ 0.5 g H ₂ O and 150 cc Solution 3 NaCl 6.3 g KBr 0.52 g H ₂ O and 150 cc Solution 4 135 g of AgNO ₃ NH ₄ NO ₃ 1 g H ₂ O was added and 450 cc solution 5 NaCl 51.7 g KBr 1.8 g H ₂ O was added and 450 cc Solution 1 was kept at 70 ° C., and 1N sulfuric acid was added to adjust the pH to 5.0. After preparation, solution 2 and solution 3 were added simultaneously over 20 minutes while vigorously stirring solution 1. Next, Solution 4 and Solution 5 were added simultaneously for 40 minutes by an accelerated addition method such that the final flow rate was three times the initial flow rate. 0.1N sulfuric acid was added in a controlled manner to keep the reactor pH constant. In the preparation of Emulsion K, when Solution 4 and Solution 5 were added, Solution 6 in which 100 mg of the next CR-compound (34) was dissolved in 200 cc of methanol was simultaneously added at a constant rate. Further, from one minute before the end of addition of the solution 4 and the solution 5 to the end thereof,
A mixed solution of 310 mg of CR-compound (19) in H ₂ O and methanol 31
Solution 7 dissolved in 0 cc was added at a constant rate.

Emulsion K thus prepared has an average grain size of 0.82 μm.
m, octahedral particles having a variation coefficient of 10%. This emulsion is 464n
It has a large light absorption peak at m and a small light absorption peak at 437 nm. Emulsion L was made in the same process as Emulsion K. However, the amount of CR-compound (34) added was 25 mg. Emulsion L is a tetrahedral grain having an average size of 0.83 μm and a coefficient of variation of 9% [(111) face 40%]. Emulsion M was made in the same process as Emulsion K. However, solution 6 in which 100 mg of CR-compound (34) was dissolved in 200 cc of methanol was added at a constant rate for 2 minutes from 3 minutes to 1 minute before the completion of addition of solution 4 and solution 5. Emulsion M
It is a cubic particle having a coefficient of variation of 0.83 μm and a coefficient of variation of 9%.

In both emulsions L and M, 310 mg of CR-compound (19) was added from 1 minute before the completion of addition of solutions 4 and 5 to the end. The addition of the dye immediately before the end of the addition did not affect the shape of the particles.

Each emulsion was chemically sensitized with diphenylthiourea and gold chloride. Table 6 shows the amounts of chemical sensitizers. After washing with water and desalting by the usual flocculation method, add gelatin and
The pH was adjusted to 6.2 and the pAg to 7.0.

Additives as shown in Table 2 were added to a triacetyl cellulose film support provided with an undercoat layer, and a protective layer was provided to prepare a light-sensitive material.

Table-2 (1) Emulsion layer ○ Emulsion ... Emulsion shown in Table-2 ○ Coupler Stabilizer: 1- (3-methylcarbamoylaminophenyl)
-2-methylcaptotetrazole Coating aid: sodium dodecylbenzenesulfonate ○ tricresyl phosphate ○ gelatin (2) protective layer ○ 2,4-dichlorotriazine-6-hydroxy-s-
Triazine sodium salt ○ Gelatin A cholera sample was exposed for sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a blue filter. Table 2 shows the obtained photographic performance results.

 The development treatment used here was performed at 38 ° C. under the following conditions.

1. Color development: 1 minute and 5 seconds 2. Bleaching ... 2 minutes 3. Rinse ... 2 minutes 4. Settle in ... 2 minutes 5. Rinse ... 2 minutes and 15 seconds 6. Stable ... 2 minutes 15 seconds The processing liquid composition used in each step is as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene 1,1-diphosphonic acid 3.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 g 3-Methyl-4- Amino-N-ethyl-N-β-hydroxyethylaniline sulfate 4.5 g Add water 1.0 pH 10.05 Bleaching solution Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1 Stabilizer Formalin 8.0 ml Add water 1 Sample that has been treated 2 shows the results obtained by measuring the concentration. The sensitivity is expressed as the reciprocal of the exposure required to give an optical density of fog + 0.2, As can be seen from Table 2, the cubic emulsion has high fog and low sensitivity when sensitized with gold and sulfur. When the amount of the gold sensitizer is increased, the fog is further increased and the sensitivity is greatly decreased. In addition, high illumination failure is also large. Grains having a (111) plane, such as a tetradecahedron or an octahedron, are hard to fog and have a high sensation when sensitized with gold sulfur. In particular, it is found that when a large amount of the gold sensitizer is used, very favorable characteristics such as an increase in sensitivity and a decrease in fog are exhibited. It can be seen that there is little high light failure.

Further, the center of development was observed in the same manner as in Example 2 using the coated samples shown in Table-2. However, the developing solution was prepared by diluting the color developing solution of this example 20-fold and treating at 20 ° C. for 1 minute. Table 2 shows CDG and EDG number ratio% and projected area ratio%.
It writes in. The effect of the present invention is clear from Table-2.

The emulsion K octahedral sulfur sensitizer 3. ⁶ × 10 ^-6 mol / mol Ag
FIG. 6 shows the results for x and the gold sensitizer 27 × 10 ⁻⁶ mol / mol Agx.

It is apparent from the figure that developed silver is formed near the vertices and edges of the octahedral grains.

Example 3 Emulsions N, O, and P were prepared in the same steps as for the emulsions K, L, and M. However, instead of CR-compound (19), CR-compound (2
The difference is that 280 mg of 1) was added and the charging temperature was lowered to 68 ° C.

CR-compounds (19) and (21) also act as spectral sensitizing dyes.

Emulsion N was octahedral, O was tetrahedral, and P was cubic, and the grain sizes were 0.66 μm, 0.65 μm, and 0.67 μm, respectively.

After desalting, chemical sensitization was performed using sodium thiosulfate and chloroauric acid, and a photographic material was prepared in the same manner as in Example 5. However, compound 4 was added in place of the stabilizer.

The following magenta coupler was used.

These light-sensitive materials were subjected to sensitometric exposure through a green filter, and developed in the same manner as in Example 2.
From the viewpoints of fog, sensitivity, and reciprocity, emulsions N and O obtained better photographic characteristics than P. Also in the case of emulsions N and O, increasing the amount of gold sensitizer gave favorable results.

Example 4 Emulsions Q, R and S were prepared in the same steps as those for the emulsions K, L and M. However, 250 mg of CR-compound (12) was added.

Emulsion Q was octahedral, R was tetrahedral, and S was cubic, and the grain sizes were 0.71 μm, 0.70 μm, and 0.71 μm, respectively. After desalting, it was chemically sensitized using sodium thiosulfate, chloroauric acid and potassium thiocyanate, and a photographic material was prepared in the same manner as in Example 2. However, the following cyan coupler was used.

These light-sensitive materials were subjected to sensitometric exposure through a red filter, followed by development in the same manner as in Example 2.

Emulsions Q and R gave favorable results in terms of sensitivity fog reciprocity, especially when the amount of gold sensitizer was increased.

Example 5 A sample, which is a multilayer color light-sensitive material having the following layers, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is obtained by the table the amount for silver halide and colloidal silver were tabulated in units of g / m ² of silver and coupler, for additives and gelatin in the unit of g / m ² , And the sensitizing dye was represented by the number of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver: 0.2 Gelatin: 1.3 Colored coupler C-1: 0.06 Ultraviolet absorber UV-1: 0.1 Same as above UV-2: 0.2 Dispersed oil Oil-1 ... 0.01 Same as above Oil-2 ... 0.01 Second layer (intermediate layer) Gelatin ... 1.0 Colored coupler C-2 ... 0.02 Dispersed oil Oil-1 ... 0.1 Third layer ( First red-sensitive emulsion layer) Emulsion (1) Described in Table 3 ... silver 1.0 Coupler C-3 ... 0.48 Coupler C-4 ... 0.56 Coupler C-8 ... 0.08 Coupler C-2 0.08 Coupler C-5 ... 0.04 Dispersed oil Oil-1 ... 0.30 Same as above Oil-3 ... 0.40 Fourth layer (second red-sensitive emulsion layer) Emulsion (2) Listed in Table 3・ ・ Silver 1.0 Gelatin ・ ・ ・ 1.0 Coupler C-6 ・ ・ ・ 0.05 Coupler C-7 ・ ・ ・ 0.1 Dispersed oil Oil-1 ・ ・ ・ 0.01 Same as above Oil-2 ... 0.05 Fifth layer (intermediate layer) Described in Table 3 Gelatin ... 1.0 Compound Cpd-A ... 0.03 Dispersed oil Oil-1 ... 0.05 Sixth layer (first green sensitive emulsion) Layer) Emulsion (3) See Table 3 ・ ・ ・ Silver 0.8 Coupler C-9 ・ ・ ・ 0.30 Coupler C-12 ・ ・ ・ 0.10 Coupler C-1 ・ ・ ・ 0.06 Coupler C-10 ・ ・ ・ 0.03 Coupler C -5 ... 0.02 Dispersed oil Oil-1 ... 0.4 7th layer (second green-sensitive emulsion layer) Emulsion (4) Described in Table 3 ... silver 0.85 gelatin ... 1.0 Coupler C-11 0.01 Coupler C-12 ・ ・ ・ 0.04 Coupler C-13 ・ ・ ・ 0.20 Coupler C-1 ・ ・ ・ 0.02 Coupler C-15 ・ ・ ・ 0.02 Dispersed oil Oil-1 ・ ・ ・ 0.20 Dispersed oil Oil-2 ・..0.05 8th layer (yellow filter layer) Gelatin ... 1.2 Yellow colloidal silver ... 0.08 Compound Cpd-B ... 0.1 Dispersed oil 1 ... 0.3 Ninth layer (first blue-sensitive emulsion layer) Emulsion (5) Described in Table 3 ... Silver 0.4 Gelatin ... 1.0 Coupler C-14 ... 0.9 Coupler C-5 ... 0.07 Dispersed oil Oil-1 ... 0.2 10th layer (second blue-sensitive emulsion layer) Emulsion (6) See Table 3 ... Silver 0.5 Gelatin ... 0.6 Coupler C-14 ... 0.25 Dispersed oil Oil-1 ... 0.07 11th layer (first protective layer) Gelatin ... 0.8 UV absorber UV-1 ... 0.1 Same as above UV-2 ... 0.2 Dispersed oil Oil-1 ... 0.01 dispersed Oil Oil-2 ・ ・ ・ 0.01 12th layer (2nd protective layer) Gelatin ・ ・ ・ 0.45 Polymethyl methacrylate particles (1.5μ in diameter) ・ ・ ・ 0.2 Hardener H-1 ・ ・ ・ 0.4 Formaldehyde scavenger S- 1 ... 0.5 Formaldehyde scavenger S-2 ... 0.5 In addition to the above components, a surfactant is applied to each layer. It was added as an agent.

Next, the chemical structural formulas or names of the compounds used in the present invention are shown below: Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate The emulsion used for sample preparation was prepared as follows.

CR-compounds (22), (23) and (24) also act as spectral sensitizing dyes.

The samples thus prepared were subjected to the treatments shown in Table 4 after exposure and aging based on JIS standards.

The processing amount of each sample was 50 m / day, and this was carried out for 16 days while replenishing the processing solution, and the test was performed after each processing solution reached a steady composition in continuous processing.

Next, the composition of each processing solution (mother liquor and replenisher) will be described.

Rinse solution Common to mother liquor and replenisher Ion exchange water 1 (Tap water is H-type strongly acidic cation exchange resin (Diaion SK-1B manufactured by Mitsubishi Kasei Co., Ltd.) and OH type strongly basic anion exchange resin (Diaion SA- 10A) through a mixed-bed column packed at a volume ratio of 1: 1.5 and treated with calcium and magnesium to 3 mg / or less) Sodium diisocyanurate 20 mg Sodium sulfate 150 mg Polyoxyethylene-p-monononyl phenyl Ether 300 mg (average degree of polymerization 10) After treatment at pH 6.5 to 7.5 or more, the same sample as that subjected to continuous treatment was treated after exposure lapse according to JIS standard.

When the ISO sensitivity of the processed film was calculated based on the JIS standard, it was confirmed that this sample had ISO ₅ O,
It was found that high silver chloride had high sensitivity which could not be reached yet.

Example 6 A sample of the color photographic material obtained in Example 5 is shown in Table-5.
In the same manner as in Example 5, except that the composition was changed to the following treatment composition, a sensitivity equivalent to approximately ISO ₅₀ was stably obtained. Further, the emulsions (1) to (6) used were processed CDG emulsions in which the development starting point was tested by the method described above.

Next, the composition of each sample solution is described.

Rinse solution Common to mother liquor and replenisher Ion exchange water 1 (Tap water is H-type strongly acidic cation exchange resin (Diaion SK-1B manufactured by Mitsubishi Kasei Co., Ltd.) and OH type strongly basic anion exchange resin (Diaion SA- 10A) through a mixed-bed column packed at a volume ratio of 1: 1.5 and treated with calcium and magnesium to 3 mg / or less) Sodium diisocyanurate 20 mg Sodium sulfate 150 mg Polyoxyethylene-p-monononyl phenyl Ether 300 mg (average degree of polymerization: 10) pH 6.5 to 7.5 Example 7 A multilayer color photographic material comprising the following layers was prepared on an undercoated cellulose triacetate film support, and used as a third green sensitive layer. Samples 1101 to 110 described below containing emulsions A and B and emulsions F and G of Example 1 in the third blue-sensitive layer as follows.
It was set to 3.

Preparation of Emulsion A In water 1, 5 g of potassium bromide, 0.05 g of potassium iodide, 30 gelatin
g, thioether compound, HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ )
_2.5 cc of a 5% aqueous solution of ₂ OH was added to the solution and kept at 75 ° C.
While stirring, an aqueous solution of 8.33 g of silver nitrate and 5.94 g of potassium bromide,
An aqueous solution containing 0.726 g of potassium iodide was added over 45 seconds by the double jet method. Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of the addition was twice that at the start of the addition. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining the potential at pAg8.1. The flow rate at this time was accelerated so that the flow rate at the end of the addition was eight times the flow rate at the start of the addition. After the addition is completed, 2N potassium thiocyanate solution 15cc
Was added, and 50 cc of a 1% potassium iodide aqueous solution was further added. Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method.After raising the temperature to 40 ° C., 68 g of gelatin, 2 g of phenol, and 7.5 g of trimethylolpropane were added, and pH 6. Adjusted to 40, pAg 8.45. After raising the temperature to 56 ° C., the CR-compound (8) of the present invention was
735 mg was added. Sodium thiosulfate pentahydrate after 10 minutes
8.2 mg, 163 mg of potassium thiocyanate and 5.4 mg of chloroauric acid were added, and after 5 minutes, it was rapidly cooled and solidified. In the obtained emulsion, 93% of the total projected area of all grains consisted of grains having an aspect ratio of 3 or more. The average projected area diameter of all grains having an aspect ratio of 2 or more was 0.83 μm, and the average thickness was 0.161.
In μm, the aspect ratio was 5.16.

Preparation of Emulsion B Emulsion A was prepared in the same manner except that the amount of CR-compound (8) added to Emulsion A was 200 mg, and 535 mg of sensitizing dye was added after chemical sensitization.

First layer: antihalation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.1 g / m ² UV absorber ^U-2 0.1 g / m 2 High-boiling organic solvent Oil-1 0.1 cc / m ² Gelatin 1.9 g / m ² second layer: middle layer-1 Cpd D 10 mg / m ² high boiling point organic solvent Oil3 40 mg / m ² gelatin 0.4 g / m ² third layer: middle layer-2 halide emulsion (average grain size 0.06Myu AgI content 1 mol%) silver 0.05 g / m ² gelatin 0.4 g / m ² layer 4: spectral first red-sensitive emulsion layer sensitizing dye S-1 and S-2 Sensitized silver iodobromide emulsion (one-to-one mixture of monodisperse cubes having an average particle size of 0.2μ and AgI content of 5 mol% and monodisperse cubes having an average particle size of 0.1μ and AgI content of 5 mol%) 0.4 g / m ² coupler C-1 0.2 g / m ² C-2 0.05 g / m ² High boiling organic solvent Oil-1 0.1 cc / m ² Gelatin 0.8 g / m ² Fifth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 AgI content of an average particle size of 0.3 micron 4 mol% of monodisperse cubic emulsion) silver 0.4 g / m ² Coupler ^{C-1 0.2 g / m 2} C-3 0.2 g / m 2 C-2 0.05 g / m 2 High Boiling point organic solvent Oil-1 0.1 cc / m ² Gelatin 0.8 g / m ² Sixth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average 0.4 μg / m ² coupler C-3 0.7 g / m ² gelatin 1.1 g / m ² 7th layer: intermediate layer-3 Dye D-1 0.02 g / m ² gelatin 0.6 g / m ² 8th layer: intermediate layer-4 fine-grained silver iodobromide emulsion with a fogged surface average particle size 0.06 μg AgI content 1 mol% silver amount 0.05 g / m ² compound CpdA 0.2 g / m ² gelatin 1.0 g / m ² 9th layer: AgI content 5 in sensitized first green-sensitive emulsion layer dye S-3 and S-4 in spectrally sensitized silver iodobromide emulsion (average particle size 0.2μ Mol% of a monodisperse cube and a monodisperse cube having an average particle size of 0.1 μg AgI content of 5 mol%
1: 1 mixture) Silver amount 0.5 g / m ² Coupler C-4 0.3 g / m ² compound CpdB 0.03 g / m ² Gelatin 0.5 g / m ² 10th layer: 2nd green-sensitive emulsion layer Sensitizing dye S- Silver iodobromide emulsion containing 3 and S-4 (monodisperse cube having an average particle diameter of 0.4 μm and an AgI content of 5 mol%) Silver amount 0.4 g / m ² coupler C-4 0.3 g / m ² compound CpdB 0.03 g / m ² gelatin 0.6 g / m ² 11th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (emulsion-A, B, A) Silver amount 0.5 g / m ² coupler C-4 0.8 g / m ² compound CPDB 0.08 g / m ² gelatin 1.0 g / m ² 12th layer: interlayer -5 dye D-2 0.05 g / m ² gelatin 0.6 g / m ² 13 Layer: Yellow filter layer Yellow colloidal silver 0.1 g / m ² compound CpdA 0.01 g / m ² Gelatin 1.1 g / m ² 14th layer: 1st blue-sensitive emulsion layer Iodine containing sensitizing dyes S-5 and S-6 Silver bromide emulsion (monodisperse cubic emulsion having an average particle size of 0.2 μAgI content of 3 mol% and an average particle size of 0.1 μAgI content of 3 mol% % Of one of monodisperse cubic emulsion: 1 mixture) silver 0.6 g / m ² Coupler C-5 0.6 g / m ² Gelatin 0.8 g / m ² 15th Layer: 2nd blue-sensitive emulsion layer Sensitizing dye S- Silver iodobromide emulsion containing 5 and S-6 (tabular grains having an average particle size of 0.5 μm and an AgI content of 1.5 mol%) Silver amount 0.4 g / m ² coupler C-5 0.3 g / m ² C-6 0.3 g / m ² gelatin 0.9 g / m ² 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (Emulsion-G, G described in Example 1) , F) silver amount 0.4 g / m ² coupler C-6 0.7 g / m ² gelatin 1.2 g / m ² 17 layer: first protective layer UV absorber U-1 0.04g / m ² UV absorber U-3 0.03 g / m ² UV absorber U-4 0.03g / m ² UV absorber U-5 0.05g / m ² UV absorber U-6 0.05g / m ² compound Cpd C 0.8 g / m ² dye D-3 0.05 g / m ² gelatin 0.7 g / m ² 18th layer: 2nd protective layer Fine grain silver iodobromide emulsion with a fogged surface (average particle size 0.06 μ Ag I content 1 mol%) Silver amount 0.1 g / m ² Polymethyl methacrylate particles (average particle size 1.5μ) 0.1 g / m ² Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5μ) 0.1 g / m ² Silicon oil 0.03 g / m ² Fluorine-containing surfactant W-1 3 mg / m ² Gelatin 0.8 g / m ^{2 In} addition to the above composition, gelatin hardener H-1 and surfactant are added to each layer did.

The sample piece 10 of the sample 101 to 103 obtained was thus ^-6
After performing wedge exposure with an exposure time of 50 seconds and an exposure time of 100 seconds, the following processing was performed to evaluate development progress of photographic characteristics and exposure time dependency.

Processing Step Time Temperature 1st development 4,6,10 minutes 38 degrees Rinse 2 minutes 38 degrees Inversion 2 minutes 38 degrees Color development 6 minutes 38 degrees Adjustment 2 minutes 38 degrees Bleaching 6 minutes 38 degrees Wearing 4 minutes 38 degrees Washing 4 minutes 38 degrees Stability 1 minute Room temperature Drying Use the following composition for the treatment solution.

First developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid / pentasodium salt 2 g Sodium sulfite 20 g Hydroquinone / monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4- Hydroxymethyl-3
Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water 1000ml Reversal water 700ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g Chloride 1st Tin (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Add water 1000 ml Color developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3 g Sodium sulfite 7 g Trisodium phosphate (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl -4-Aminoaniline / sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Add water 1000ml Adjustment solution Water 700ml Sodium sulfite 12g NaEthylenediaminetetraacetate Lithium (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Add water 1000 ml Bleaching solution Water 800 ml Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ammonium iron (III) ethylenediaminetetraacetate (dihydrate) 120 g Potassium bromide 100 g of water was added and 1000 ml of fixing solution water 800 ml of sodium thiosulfate 80.0 g of sodium sulfite 5.0 g As a result, the sensitivity of the third green-sensitive layer was higher for 1101 than for sample 1102, and the development proceeded quickly. 11 for sample 1103
In No. 01, the sensitivity of the third blue-sensitive layer was high, and the decrease in sensitivity at high illuminance exposure was small.

5.0 g of sodium bisulfite and 1000 ml of water Stabilized water 800 ml of formalin (37% by weight) 5.0 ml Fuji Drifel L (surfactant manufactured by FUJIFILM Corporation) 5.0 ml 1000 ml of water and 1,000 ml Minimum concentration of magenta and yellow From2.0
The color reversal sensitivities of the third green-sensitive layer and the third blue-sensitive layer were estimated based on the large relative exposure.

Structure of the compound used in Example 11

[Brief description of the drawings]

1 and 2 show samples -6 and-of Example 1, respectively.
7 is an electron micrograph showing a development start point of silver halide crystal grains in a silver halide emulsion of No. 7;
It is twice. FIG. 3 is an electron micrograph showing the starting point of the development of silver halide crystal grains of Emulsion K of Example 2, with a magnification of 12,0.
It is 00 times.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Sumito Yamada 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd. (56) References JP-A-61-93447 (JP, A) JP-A-58-108526 (JP, A) JP-A-59-133540 (JP, A) JP-A-59-162540 (JP, A) JP-A-62-27040 (JP, A) JP-A-58-126526 (JP, A) JP-A-61-205929 (JP, A) JP-A-62-89948 (JP, A) JP-A-62-124551 (JP, A) JP, A) JP-A-55-121432 (JP, A) JP-A-63-305343 (JP, A) JP-B-6-93080 (JP, B2) "Chemistry of Photography," Akira Sasai, March 1982 Published on March 5, Photographic Industry Publishing Company, pages 86-87

Claims (2)

(57) [Claims] 1. A method comprising dispersing silver halide grains in a dispersion medium.
In silver halide photographic emulsions, the silver halide grains
Have (111) plane and no epitaxial growth site
Normal crystal grains during chemical sensitization or chemical
Prior to the sensitization step, they are represented by the following general formulas [I] to [V].
Of compounds selected from the group of compounds and nucleic acids
It is prepared by adding at least one kind and has the (111) face.
At least 50% of the silver halide grains (projected area) are: a) Development starts at or near the vertex of the grain ridge
And / or b) so that development is initiated at or near the ridges of the particles.
A silver halide photographic emulsion characterized in that the grains are controlled.Where Z₁₀₁And Z₁₀₂Are the elements necessary to form each heterocyclic nucleus.
Represents the gang. R₁₀₁And R₁₀₂Represents an alkyl group, an alkenyl group,
Represents a quinyl group or an aralkyl group. m₁₀₁Represents a positive number of 0 or 1, 2 or 3. However,
m₁₀₁If represents 1₁₀₃Is hydrogen atom, lower alkyl
Aralkyl group and aryl group. R₁₀₄Represents a hydrogen atom. Where m₁₀₁Represents 2 or 3
If you do, R₁₀₃Is a hydrogen atom and R₁₀₄Is a hydrogen atom, low
Represents a lower alkyl group or an aralkyl group;₁₀₂Concatenate with
To form a 5- or 6-membered ring,₁₀₁But 2
Or 3 for R₁₀₄Represents a hydrogen atom, R₁₀₃Is
Other R₁₀₃To form a hydrocarbon or heterocyclic ring
Is also good. j₁₀₁, K₁₀₁Represents 0 or 1. X₁₀₁ Represents an acid anion. n₁₀₁Represents 0 or 1.Where Z₂₀₁, Z₂₀₂Is Z₁₀₁Or Z₁₀₂Is synonymous with R₂₀₁, R₂₀₂Is R₁₀₁Or R₁₀₂Is synonymous with R₂₀₃Is alkyl, alkenyl, alkynyl or aryl
Represents a radical. m₂₀₁Represents 0, 1, or 2. R₂₀₄Represents a hydrogen atom, a lower alkyl group or an aryl group
And m₂₀₁Represents 2₂₀₄And R₂₀₄And connected
It may form a hydrocarbon ring or a heterocyclic ring. Q₂₀₁Is a sulfur atom, oxygen atom, selenium atom or> NR
₂₀₅Represents R₂₀₅Is R₂₀₃Is synonymous with j₂₀₁, R₂₀₁, X₂₀₁ And n₂₀₁Is j₁₀₁, K₁₀₁,
X₁₀₁ And n₁₀₁Is synonymous withWhere Z₃₀₁Represents an atomic group necessary for forming a heterocyclic ring. Q₃₀₁Is Q₂₀₁Is synonymous with R₃₀₁Is R₁₀₁Or R₁₀₂And R₃₀₂Is R₂₀₃Is synonymous with m₃₀₁Is m₂₀₁Is synonymous with R₃₀₃Is R₂₀₄Synonymous with m₃₀₁When represents 2 or 3
Is R₃₀₃And other R₃₀₃Is linked to form a hydrocarbon ring or a heterocyclic ring
It may be formed. j₃₀₁Is j₁₀₁Is synonymous withIn the formula, Y is a sulfur atom or an oxygen atom. Z₁Is saturated or unsaturated with sulfur or oxygen atoms
Represent the atoms required to form a heterocyclic ring of
An elementary ring may have a substituent, and a heterocyclic ring may be condensed with another ring.
They may combine to form a condensed ring. General formula [V] R₁-S- (V)_m-Y-R_Two In the formula, X is a divalent organic group, and alkylene, arylene, a
Lucenylene, -SO_Two-, -SO-, -O-, -S-, -C
(= 0)-, -N (R_Three)-Alone or in combination
Is done. Also, alkylene, arylene, alkenylene
Is R₁May have the substituents described above. R_ThreeRepresents a hydrogen atom, an alkyl group, or an aryl group. m is 0 or 1. R₁Is hydrogen atom, alkali metal, alkaline earth metal, substitution
Or an unsubstituted alkyl group, a substituted or unsubstituted
Represents a reel group or a substituted or unsubstituted heterocyclic group. R_TwoIs a hydroxy group, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted
Heterocyclic group, substituted or unsubstituted amino group, alkoxy
Represents a silyl group or an aryloxy group. R is a substituent₁When
Similar things are possible. Y is -CO or -SO_TwoRepresents 2. The silver halide grain is a normal crystal grain having a (111) plane, has a (111) plane, is coated on a support, and has a characteristic curve obtained by developing. Among the silver halide grains contributing to image formation at a density between [maximum density-minimum density] × 3/4 and maximum density + 0.2, at least 50% (projected area) of the grains are a) grains and / or 2. The silver halide photographic emulsion according to claim 1, which is b) grains.