JPH03188436A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high sensitivity and high contrast and to improve safelight safety by using a silver chlorobromide emulsion which is obtd. by chemical senstization of the surface and in which >=95mol% is a silver chloride and a silver iodide is substantially not contained. CONSTITUTION:The halogen compsn. of silver halide particles consist of the silver chlorobromide in which >=95% of the total silver halide constituting the silver halide particles is the silver chloride and the silver iodide is substantially not contained. The silver halide particles have the locally existing phases exceeding at least 10mol% in the silver bromide content. Further, the silver halide particles are maintained in an atmosphere of >=6.5 pH in the stage for forming the locally existing phases of the high content of the silver bromide and the chemical sensitization stage for the surfaces. Thus, the suitability to rapid processing and the high sensitivity and high contrast are obtd. In addition, the safelight safety and preservable property of latent images are improved.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it is suitable for rapid processing, has high sensitivity, high contrast, is excellent in safelight safety, and has a long latent image preservation property. The present invention relates to a silver halide photographic material having good properties. (Prior Art) Currently commercially available silver halide photographic materials and image forming methods using the same are diverse and are used in all fields. The halogen composition of the silver halide emulsions used in many of these light-sensitive materials, especially in the case of photographic materials, is often silver iodobromide, which is mainly composed of silver bromide, in order to achieve high sensitivity. . On the other hand, in products used in markets where there is a strong demand for completing large quantities of prints in a short lead time, such as light-sensitive materials for color photographic paper, it is necessary to speed up the development process, so the use of bromide containing virtually no silver iodide is required. Silver or silver chlorobromide is used. In recent years, there has been an increasing demand for improved rapid processing performance of color photographic paper, and much research has been conducted. It is known that increasing the silver chloride content of the silver halide emulsion used dramatically improves the development speed. However, silver halide emulsions with a high silver chloride content are difficult to obtain high sensitivity and sharp gradations, and they also have the disadvantage of reciprocity failure, that is, large changes in sensitivity and gradation due to changes in exposure illuminance. It is known. Various techniques have been disclosed to overcome the above-mentioned drawbacks of silver halide emulsions with a high silver chloride content. JP-A-64-26837 discloses that high sensitivity, high contrast, and stable performance can be obtained by using a high silver chloride emulsion having a silver bromide-rich slope near the apex of the grain. JP-A-1-105940 discloses that an emulsion with excellent reciprocity properties without impairing latent image stability for several hours after exposure is produced by using a high silver chloride emulsion having a silver bromide-rich region selectively doped with iridium. It is disclosed that it can be obtained. The present inventors subsequently continued intensive studies in order to further dramatically improve the performance of high silver chloride emulsions. As a result, when a high silver chloride emulsion prepared as described above is used as a light-sensitive material, the gradation becomes softer if the light-sensitive material is exposed to safelight light before printing, and furthermore, it is difficult to print out. It has become clear that the stability of the latent image over a long period of several days is not necessarily satisfactory. If this happens, not only will the photosensitive material be difficult to handle in a laboratory, but the quality of the finished print may also be degraded. The inventors have discovered that by gold sensitizing high silver chloride emulsions, long-term latent image stability is significantly improved. However, depending on how it is used, gold sensitization can cause gradations to become softer, and it can also worsen the stability of the emulsion and light-sensitive material over time before coating, so the advantages of the high-silver chloride emulsion mentioned above cannot be fully realized. was something that could not be used. (Problem to be Solved by the Invention) Therefore, the object of the present invention is to provide a method suitable for rapid processing, high sensitivity,
The present invention relates to a silver halide photographic material that has high contrast, excellent safelight safety, and good latent image storage properties over a long period of time. (Means for Solving the Problems) An object of the present invention is to provide a silver halide photographic material having at least one photosensitive emulsion layer on a support, in which the silver halide emulsion contained in the emulsion layer is a silver halide emulsion. At least 10 mol% silver bromide content near the surface of the grains
is a silver chlorobromide emulsion substantially free of silver iodide, in which 95 mol% or more is silver chloride, obtained by chemically sensitizing the surface after forming a localized phase exceeding This was achieved by using a silver halide photographic light-sensitive material, which is an emulsion that is aged in an atmosphere with a pH of 6.5 or higher from the start of formation to the end of chemical sensitization of the surface. The halogen composition of the silver halide grains of the present invention must consist of silver chlorobromide containing substantially no silver iodide, in which 95 mol% or more of the total silver halide constituting the silver halide grains is silver chloride. be. Here, it means that it does not substantially contain silver iodide.
This means that the silver iodide content is 1°0 mol% or less. A preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, in which 98 mol % or more of the total silver halide constituting the silver halide grains is silver chloride. The silver halide grains of the present invention must have a localized phase of at least 10 mol % in terms of silver bromide content. In order to exhibit the effects of the present invention, the localized phase having a high silver bromide content must be located near the grain surface from the viewpoint of pressure resistance, treatment liquid composition dependence, etc. The term "near the grain surface" as used herein refers to a position within 115 mm of the grain size of the silver halide grain used, as measured from the outermost surface. The position is preferably within 1/10 of the grain size of the silver halide grains used, as measured from the outermost surface. The most preferable arrangement of the localized phase with a high silver bromide content is one in which a localized phase with a silver bromide content of at least 10 mol % is epitaxially grown in a corner part of cubic or tetradecahedral silver chloride grains. . The silver bromide content of the localized phase with high silver bromide content is 10 mol%
However, if the silver bromide content is too high, it may cause desensitization when pressure is applied to the photosensitive material.
Variations in the composition of the processing solution may impart unfavorable characteristics to the photographic material, such as large changes in sensitivity and gradation. Taking these points into consideration, the silver bromide content of the localized phase with a high silver bromide content is calculated as follows:
A range of 0 to 60 mol% is preferred, and a range of 20 to 50 mol% is most preferred. The silver bromide content of the localized phase with a high silver bromide content can be determined using the X-ray diffraction method (for example, described in [Nihon Kagaku Complete Edition, New Experimental Chemistry Course 6, Structural Analysis] Maruzen), etc. can be analyzed. The localized phase having a high silver bromide content is preferably composed of 0.1 to 20% of silver, and 0.5 to 7% of the total silver amount constituting the silver halide grains of the present invention. More preferably, it is made of silver. The interface between such a localized phase with a high silver bromide content and other phases may have a clear phase boundary, or may have a transition slope where the halogen composition gradually changes. good. Various methods can be used to form such a localized phase with a high silver bromide content. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, the localized phase can also be formed using a conversion method in which silver halide grains that have already been formed are converted into silver halide having a lower solubility product. However, by mixing cubic or tetradecahedral silver halide host grains with silver halide fine grains that have a smaller average grain size and a higher silver bromide content than the silver halide host grains, and then ripening them, the bromide The localized phase with high silver content is formed by
This is most preferable in terms of exhibiting the effects of the present invention. The formation of a localized phase with a high silver bromide content is preferably carried out in the presence of an iridium compound. Here, forming a localized phase in the presence of an iridium compound means supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver or halogen to form a localized phase. say. When a localized phase with a high silver bromide content is formed by mixing and ripening silver halide fine grains that have a smaller average grain size than the silver halide host grains and a higher silver bromide content. Most preferably, silver halide fine particles having a high silver bromide content contain an iridium compound in advance. An iridium compound may be present during phase formation other than the formation of a localized phase with high silver bromide content, but the localized phase with high silver bromide content is formed with at least 50% of the total iridium added. It is preferable. Most preferably, it is formed with at least 80% of the total iridium added. In the present invention, after the formation of a localized phase with a high silver bromide content,
It is necessary to chemically sensitize the surface. As the chemical sensitization, it is preferable to carry out sulfur sensitization, but it is also preferable to use gold sensitization, reduction sensitization, etc. in combination. Chemical sensitization with sulfur used in the present invention is performed using sulfur-containing compounds (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin or silver.
This is done using Specific examples of these can be found in U.S. Patent No. 1.
No. 574.944, No. 2,278.947, No. 2
．． It is described in specifications such as No. 410.689, No. 2,728.668, and No. 3,656.955. In the present invention, it is necessary to carry out ripening in an atmosphere having a pH of 6.5 or more between the start of formation of a localized phase with a high silver bromide content and the end of chemical sensitization of the surface. If the pH is too high, it may cause unintended fogging, so it is preferably 9.0 or less. The effects of the present invention include p
H is more preferably in the range of 6.8 or more and 8.0 or less, and 7.
The most preferred range is 0 or more and 7.7 or less. Aging in an atmosphere with a pH of 6.5 or higher may be carried out only when a localized phase with a high silver bromide content is formed, or may be carried out only when chemically sensitizing the surface. In addition, it is also possible to ripen in an atmosphere of pH 6.5 or higher for a part of the time during the formation of a localized phase with a high silver bromide content or chemical sensitization of the surface, or by dividing it into several times. You can do it. However, in order to make the effects of the present invention even more remarkable, it is necessary to adjust the temperature to pH 6,
It is preferable to maintain an atmosphere of 5 or more. The silver halide grains of the present invention may have (100) planes, (111) planes, or both planes on their outer surfaces; may include higher-order planes, but is preferably a cube or a tetradecahedron mainly consisting of (100) planes. The size of the silver halide grains of the present invention may be within the commonly used range, but the average grain size is from 0.1 μm to 1.0 μm.
Preferably, the thickness is 5 μm. The particle size distribution may be polydisperse or monodisperse, but monodisperse is preferable. The particle size distribution, which represents the degree of monodispersity, is defined as the ratio of the statistical standard deviation (s) to the average particle size (d) (s/
d) is preferably 0°2 or less, more preferably 0.15 or less. It is also preferable to use a mixture of two or more types of monodispersed emulsions. Spectral sensitization is performed for the purpose of imparting spectral sensitivity to the emulsion of each layer in the light-sensitive material of the present invention in a desired light wavelength range. This is preferably carried out by adding a spectral sensitizing dye, which absorbs the spectral sensitizing dye. Examples of the spectral sensitizing dye used in this case include F. M. llarm@r 11
eterocyclic compounds-Cya
nine dies and related com
pounds (John Wiley & 5ons
(New York, London), 1964
2013). Examples of specific compounds and spectral sensitization methods are f14) Page 22, upper right column of the specification of JP-A-62-215272~
The one described on page 38 is preferably used. The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72vi of the specification of JP-A-62-215272 mentioned above are preferably used. In the emulsion used in the present invention, the latent image mainly has the general formula (
C-11) 01

[When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. Couplers are commonly used. The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention are as follows - Saito (C-1), (C-11), (M21), (M-11)
and (Y). General formula (C-1) 11 General formula (M-1) General formula (M-n) Y! Ichika formula (Y) In general formulas (C-1) and (C-11), Rls
Rt and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, Rs and R- represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R8 represents R8 It may also represent a group of nonmetallic atoms that together form a nitrogen-containing 5Fl ring or a 6-membered ring.
Y8, Y represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent; n represents 0 or 1; R% in general formula (C-■) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, jerk-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, pukunamidomethyl group, and methoxymethyl group. Preferred examples of the cyan coupler represented by -Funenin (C-1) or (C-11) are as follows. In the general formula (C-[), preferable R1 is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group. -a When R1 and R8 do not form a ring in formula (C-1), R3 is preferably a substituted or Zta-free alkyl group or aryl group, particularly preferably a 110 aryloxy-substituted alkyl group, and Rs is preferably a hydrogen atom. In general formula (C-11), R4 is preferably ff1A or an unsubstituted alkyl group or aryl group, and particularly preferably an alkyl group with substituted aryloxy position IA. In the one-claw type (C-n), R5 preferably has 2 to 1 carbon atoms.
It is a methyl group having 5 alkyl groups and a substituent having 1 or more carbon atoms, and the substituted tA group is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. - In Shipman (C-n), RS is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. - Preferred R6 in Shipman (C-11) is a hydrogen atom,
A halogen atom, with a chlorine atom and a fluorine atom being particularly preferred; - Preferred Y in Funato (C-1) and (C-It), and Y are a hydrogen atom, a halogen atom, an alkoxy group, and an aryloxy group, respectively; , acyloxy group, and sulfonamide group. -FQ In formula (M-1), P and R9 represent an aryl group, P represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl convex group, and Y represents hydrogen Represents an atom or su leaving group. Aryl group (preferably phenyl group) of R1 and R,
The substitutions tA groups allowed for substituent R1 are the same as '; It, IA G, and two or more substitutions t
When there is a ^ group, it may be the same or different a R1
is preferably a hydrogen atom, an aliphatic acyl group or a convex sulfonyl group, particularly preferably a hydrogen atom. Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in US Pat. No. 4.3.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51,897 and International Publication No. W○88104795. In Formula 119 (M-11), R1° represents a hydrogen atom or a substituent, Y4 represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferred.
a, Zb and Zc are methine, ZIAmethine, =N-
or -Nl+-, and the Za -Zb bond and Zb -Z
One of the c bonds is a double bond and the other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, including when it is part of an aromatic ring, when R1° or Y4 forms a dimer or more multimer, and when Za, Zb or When Zc is a substituted methine, it includes the case where the substituted methine forms a dimer or more multimer. Among the pyrazoloazole couplers represented by the formula (M-It), imidazo(1), which is described in U.S. Pat. , 2-b) pyrazoles are preferred, and the pyrazolo(1,5'-b)(1,2,4) triazoles described in U.S. Pat. No. 4,540,654 are particularly preferred. In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, especially n
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in No. 147254/1983, and pyrazoloazole couplers with a ballast group at the 6-position as described in European Patent (Publication) No. 226.849 and European Patent No. 294.785. It is preferred to use pyrazolotriazole couplers having an alkoxy group or an aryloxy group. In the general formula (Y), Ro represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group,
R8□ represents a hydrogen atom, a halogen atom or an alkoxy group, A represents -NHCOR+s, provided that R1
2 and RI4 each represent an alkyl group, an aryl group, or an acyl group, Ys represents a leaving group, R1, and R1f
The substituents for f % RI4 are the same as those allowed for R, and the leaving group Ys is preferably of the type that leaves at either an oxygen atom or a nitrogen atom; Particularly preferred are molds. General formula (C-1), (C-■), (M-1), (M-■
) and (Y) are listed below. (C-1) C, H9 Shi! (C-4) 11 (C-9) 11 (C-10) (C-12) Shi! (C-6) Cz If s Shi2 (C-7) (C-O) C! II % (C-13) (C-14) (C-15) (C-17) (C-18) (C-19) (M-1) (M-2) (M-3) I 1 I I 2 (C-20) (C-21) (C-22) (M-4) CM-6) l (M-7) (M-8) 2 (Y-1) (Y-2) (Y-5) (Y-6) (Y-3) υ11 (Y-4) (Y-7) (Y-8) (Y-9) The color photographic material of the present invention has a blue color on the support. A sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated one by one (in each layer).
M can be made. In general color photographic paper, the layers are usually coated on the support in the order listed above, but they may be coated in a different order. It is used in place of at least one of the above emulsion layers. These light-sensitive emulsion layers can include:
A silver halide emulsion sensitive to each wavelength range,
Subtractive color reproduction can be achieved by containing so-called color couplers that form dyes complementary to the sensitive light, ie, yellow for I7, magenta for green, and cyan for red. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above. The couplers represented by Saito (C-1) to (Y) above are:
In the silver halide emulsion layer constituting the photosensitive layer, there is usually 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol. In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be used.Usually, the coupler can be added by an oil-in-water dispersion method known as an oil protection method. After dissolving, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer lik method. The low-boiling point IF8 medium may be removed from the coupler dispersion by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion. As a dispersion medium for such a coupler, the dielectric constant (25℃)
2 to 20, a high boiling point it9 medium with a refractive index (25°C) of 1.5 to 1.7 and/or a water-insoluble polymer compound (in the formula,
h, h and 6 each represent an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group of ItA or IA, and 144 is Wl, 0I41 or 5-14. , n is an integer from 0 to 5, and when n is 2 or more, If is the same or different from each other (, -C In formula (E), ka and 6 represent a fused ring. may be formed). The high boiling point i solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. High boiling point *The boiling point of the solvent is preferably 160°C or higher, more preferably 170°C or higher. For details on these high boiling point organic solvents, please refer to JP-A-Sho (i.
2-215272 Publication Specification, page 137, lower right corner - 1
It is written in the upper right column of page 44. These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but organic solvent-soluble polymer. Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088100723 are used, and acrylamide-based polymers are particularly preferred from the viewpoint of color image stabilization. Using the present invention 0. The photosensitive material produced may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Also usable are gold B complexes represented by (bissalicylaldoximado)nickel complexes and (bis-N,N-dialkyldithiocarbamado)nickel complexes. Specific examples of anti-fade agents are described in the following patent specifications: Hydroquinones are U.S. Patent Section 2.360.290;
Same No. 2.418.613, same! No. 2,700,453, No. 2.701.197, No. 2.728,659
No. 2,732.300, No. 2.735.76
No. 5, No. 3.982.944, No. 4.430.4
25, British Patent No. 1.363.921, U.S. Patent Section 2.710,801, U.S. Patent No. 2.816.028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are U.S. Patent Section 3.432.30
No. 0, No. 3.573,050, No. 3.574.6
No. 27, No. 3,698°909, No. 3.764.
No. 337, JP-A No. 52-152225, etc., and spiroindanes are described in U.S. Patent Section 4,360.589, P-
Alkoxyphenols are U.S. Patent Section 2,735.76
No. 5, British Patent Tube No. 2.066, No. 975, JP-A-59-
No. 10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Pat.
No. 35, Japanese Patent Publication No. 52- (i (I23, etc.), gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent Sections 3.457.0-9 and 4.332,886, respectively. , Japanese Patent Publication No. 56-21144, etc., hindered amines are disclosed in U.S. Patent Section 3.336.1.
No. 35 1. No. 4.268,593゜, British Patent Tube 1
．． No. 326.889, No. 1,354.313, No. 1.410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 114036-1987, No. 59-53846, @59-78344 No. 4, etc., metal complexes are covered under Section 4 of the U.S. Patent.
, 050,938, 4.241°155, and British Patent No. 2.027.731 (^), respectively. These compounds usually contain 5 to 1001'I! for each corresponding color coupler. The objective can be achieved by co-emulsifying m% with the coupler and adding it to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and both sides adjacent thereto. As ultraviolet absorbers, benzotriazole compounds WIA'ed with aryl groups (eg, U.S. Patent Section 3.533.
794), 4-thiazolidone compounds (e.g., U.S. Pat. Nos. 3.314.794 and 3.352)
, No. 681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid esters, compounds (e.g., those described in U.S. Pat. No. 3,705.80),
No. 5, ゛Same No. 3.70? , No. 395), bucdiene compounds (-p, @, IS, door, as described in U.S. Pat. 406.OTO issue s, 6tt, sn
4.271,307) can be used. A UV-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or a UV-A absorbing polymer may be used, and these UV-A absorbers may be mordanted in a specific layer. Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred. In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers. That is, a compound (CF) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aromatic compound remaining after color development processing. For example, the use of a compound (G) that chemically bonds with the oxidized form of an amine-based color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, for film storage after processing. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the remaining color developing agent or its oxidized product and the coupler. Preferred compounds (F) have a second-order reaction rate constant km (in trioctylbosphate at 80°C) with p-anisidine of 1.01/mol-sec to I
X10-'J! It is a compound that reacts in the range of /mol·sec. Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545. When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if kg is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow (as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent.Such compound CF ) can be represented by the following -Seaman (Fri or (Fn)) General formula (Fl) R+ (A), -X General formula (Fll) R, -C-Y In the quantitative formula , R3, and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n represents 1 or 0. A represents a group that reacts with an aromatic amine developer to form a chemical bond; , X reacts with an aromatic amine developer to form l
1iIII represents a leaving group, B is a hydrogen atom, an aliphatic group,
Y represents an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents an aromatic amine developing agent with the general formula (F■)
R3, XSY, and R8 or B may be bonded to each other to form a cyclic structure. Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction. -i For specific examples of compounds represented by formulas (Fl) and (F■), see JP-A-63-158545 and JP-A-62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred. On the other hand, more preferable compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are as follows - Funato ( Gl). General formula (CHI) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z is a nucleophilic group or a nucleophilic group that is decomposed in the photosensitive material to release a nucleophilic group. Compounds represented by -Funenin (G1), which represent the group Z
(R, G, Pearson, eL al,, J
, Am. Chew, Soc, p. 319 (1968))
is preferably 5 or more, or a group derived therefrom. -a For specific examples of the compound represented by formula (CI), see European Patent Publication No. 255722, JP-A-62-1430.
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred. Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589. The photosensitive material produced using the present invention contains a water-soluble dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation and halide silane. Such dyes which may be used include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is preferable to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin manufacturing method can be found in The Macromolecular Chemistry of Gelatin, written by Arthur Weiss. Press, published in 1964). As the support used in the present invention, transparent films such as cellulose nitrate filters and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used.For the purpose of the present invention, reflective supports are used. The "reflective support J" used in the present invention is more preferably used in the present invention, and refers to one that enhances reflectivity to make the dye image formed in the silver halide emulsion layer clearer. In this method, a support is coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate, or a hydrophobic resin containing a dispersed light-reflecting substance is used as a support. For example, transparent supports with a reflective layer or a reflective material, such as glass, polyethylene terephthalate, cellulose triacetate, etc. Alternatively, there are polyester films such as cellulose nitrate, urinamide films, polycarbonate films, polystyrene films, vinyl chloride resins, etc.Other reflective supports include supports with specular reflective or type 2 diffuse reflective metal surfaces. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is better (and it is better to roughen the metal surface or use metal powder to make it diffusely reflective!) For the extra pressure, use aluminum, tin, silver, magnesium or an alloy thereof, The surface may be a metal plate, a metal foil, or a total 8.m layer surface obtained by rolling, vapor deposition, plating, etc. Among these, a metal surface obtained by vapor deposition of metal on another substrate is preferable. It is preferable to provide a waterproof resin layer, particularly a thermoplastic resin layer, on the support.9 It is preferable to provide an antistatic layer on the side opposite to the metal surface of the support of the present invention. For details, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc. These supports can be appropriately selected depending on the purpose of use. As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol. The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically calculated by dividing the observed area into adjacent unit areas of 6μ x 6μ and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (R1) of fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio of the standard deviation S of R1 to the average value (R) of R5.
/R can be obtained. The number (n) of target unit areas is preferably 6 or more, and therefore the coefficient of variation S/π can be determined by. In the present invention, the coefficient of variation of the area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the property is substantially "uniform". It can be said that The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water-washing treatment (or stabilization treatment). Bleaching and fixing may be performed separately instead of in one bath as described above. . The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotriene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −[β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above P-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6). In addition, these P-phenylenediamine F4 bodies, sulfates, hydrochlorides,! The amount of the aromatic primary amine developing agent, which may be a salt such as [li'Vs acid salt, P-)luenesulfonate salt, etc., is preferably about 0.1 per 12 developer solutions.
g to about 20 g, more preferably about 0.5 g to about Log. In carrying out the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol, where "substantially free" means preferably a developer solution containing no benzyl alcohol.
The benzyl alcohol concentration is 1 or less, more preferably 0.5d11 or less, and most preferably contains no benzyl alcohol at all. The developer used in the present invention must be substantially free of sulfite ions. More preferably, the sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized developing agent to reduce the dye formation efficiency. This is presumed to be one of the causes of increased fluctuations in photographic properties due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0XIO "1 mol/2 or less, and most preferably !It: Contains no sulfate ions. However, in the present invention, a very small amount of sulfite is added to prevent oxidation of the processing agent kit in which the developing agent is concentrated before being mixed into the solution used. Preferably, the developer solution used in the present invention is substantially free of sulfite ions, and more preferably substantially free of hydroxylamine, since hydroxylamine is present in the developer solution. This is because it functions as a preservative and has 11ZJ image activity itself, and fluctuations in the concentration of hydroxylamine are considered to have a strong influence on photographic properties. In this case, "containing substantially no hydroxylamine" means "substantially no hydroxylamine" The hydroxylamine concentration is preferably 5.0 x 10-' mol/2 or less, and most preferably it does not contain any hydroxylamine. It is more preferable to contain an organic preservative instead of the organic preservative.The organic preservative is added to the processing solution for color photographic light-sensitive materials to slow down the deterioration rate of the aromatic primary amine color developing agent. It refers to all compounds that have the function of preventing color developing agents from being oxidized by air. , hydrazines, hydrazides, phenols, α-hydroxyketone neck, α-aminoketones, t
Particularly effective organic preservatives include monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. These are JP-A-6
No. 3-4235, No. 63-30845-, No. 63-2
No. 1647, No. 63-44655, No. 63-5355
No. 1, No. 63-43140, No. 63-56654,
No. 63-58346, No. 63-43138, No. 63
-146041, 63-44657, 63-4
No. 4656, U.S. Patent No. 3.615.503, U.S. Patent No. 2.
494.903, JP-A-52-143020, JP-B-48-30496, etc. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, which may optionally contain aromatic polyhydroxy compounds described in No. 746,544, etc.
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added. Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc.; Also, the use of the above hydroxylamine derivative or hydrazine derivative in combination with amines is useful for color development. It is more preferable from the viewpoint of improving the stability of the liquid and further improving the stability during continuous processing. Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300. In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain Xl0-1 to 1.5 Xl0-' mol/2, particularly preferably 4X10-'' to lXl0
-'mol/l. Chlorine ion concentration is 1.5X10-
If the amount exceeds 10-1 mol/2, it has the disadvantage of delaying development and is not preferable in achieving the object of the present invention of rapid development and high maximum density.
- If the amount is less than 3.0 mole/2, it is not preferable in terms of preventing fog.
It is preferable to contain X10-'mol/N-1.0X10-comole/2, more preferably S,
~5X10-'mol/j! It is. Bromine ion concentration is l
If it is more than Xl0-3 mol/2, the development will be delayed and the maximum density and sensitivity will be reduced, and if it is less than 3.0X10-' mol/E, capri cannot be sufficiently prevented. The chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the light-sensitive material into the developer during the development process. When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride. Alternatively, it may be supplied from an optical brightener added to the developer. Substances that supply bromide ions include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and krillam bromide. Among these, preferred are potassium bromide and sodium bromide. When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion. The color developer used in the present invention is preferably ρ11
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds. In order to maintain the above pH, it is preferable to use various buffering agents. Examples of the buffering agents include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyamitumecun salt, lysine salt, etc. can be used. Especially carbonates, phosphates, tetraborates, hydroxybenzoates are soluble, pl+ 9
．． These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or higher, having no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and being inexpensive. is particularly preferred. Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate J4, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boron potassium tetraborate, sodium tetraborate (sand), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. can be mentioned. However, the present invention is not limited to these compounds. The amount of the slow-moving i agent added to the color developer is 0.1 mol/
It is preferably 1 or more, especially 0.1 mol/2 to 0
．． Particularly preferred is 4 mol/2. In addition, various caloric acid agents can be used in the color developer to prevent precipitation of calcium and magnesium, or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'
-tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamineol I-hydroxyphenylacetic acid, 2-phosphonobutane-1
,2,4-)licarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N. Examples include N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be as long as it is sufficient to sequester the metal ions in the color developer. For example, 12
It is about 0.1g to Log per unit. Any development accelerator can be added to the color developer if necessary. As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
．． 247, etc., P-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-52-1989-
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
6-156826 and 52-43429, etc., and US Pat. No. 2.494.
No. 903, No. 3.128.182, No. 4,230,7
No. 96, No. 3,253,919, Special Publication No. 41-114
3.1, U.S. Patent No. 2,482,546, U.S. Pat.
96,926 and 3,582,346, etc.; Japanese Patent Publication No. 37-16088, 42-
25201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532゜501, etc., and other 1-phenyl-3-pyrazolidones. etc., imidazoles, etc. can be added as necessary. In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic anti-capri agents include benzotriazole, 6-nidropenzimiguzole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzole. Typical examples include nitrogen-containing heterocyclic compounds such as imidazole, 2-thiazolylmethyl-benzimiguzole, indazole, hydroxyazaindolizine, and adenine. It is preferable that the color developer that can be used in the present invention contains a fluorescent whitening agent.
-Diamino-2,21-disulfostilbene compounds are preferred, and the amount added is O~5g/7! Preferably 0.1g
~471. Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary. The processing temperature of the color phenomenon liquid that can be used in the present invention is 20~
50°C, preferably 30-40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The smaller the amount of replenishment, the better, but it is 20 to 60 per photosensitive material.
0d is suitable, preferably 50-300d. More preferably 60 m1 to 20 M, most preferably 60 m
m1 to 150m. Next, a desilvering process that can be applied to the present invention will be explained. The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step. The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below. As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
III) with 8!1 complex salts (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, bosoccarboxylic acid, and complex salts with q-i phosphonic acid) or citric acid, Preferred are organic acids such as tartaric acid and malic acid; persulfates; and hydrogen peroxide. Among these, organic complex salts of iron (I[I) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. ) aminopolycarboxylic acids useful for forming organic complex salts of
Aminopolyphosphonic acid or [5 phosphonic acid or their salts are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts; among these compounds, iron salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid; (I[l) complex salt is preferable because it has a high bleaching edge. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as 7-minopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid.
Aminopolycarboxylic acid iron complexes are preferred among iron complexes, which may be used in excess to form an iron ion complex salt, and the amount added is 0.01 to 1.0 mol/2, preferably 0.05 to 1.0 mol/2. It is 0.50 mol/2. Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. See, for example, U.S. Pat. Specification No. 812, JP-A-53-95
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706.561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties. In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more inorganic substances having ρII 11 fli ability such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-sithia-1,8-octanediol, and other water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of 211 or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate In particular, it is preferable to use ammonium thiosulfate salt, and the amount of fixing agent per 1ffi is preferably 0.3 to 2 mol, more preferably 0.5 mol.
~1.0 mol. bleach-fix or fixer p
The Hel range is preferably 3 to 10, more preferably 5 to 9. Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. It is preferred to contain a sulfite ion releasing compound such as a metabisulfite (eg, potassium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.). 02～
The gold content is preferably 0.05 mol/f, more preferably 0.04 to 0.40 mol/2. Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added. Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary. After silver processing such as fixing or bleach-fixing, washing with water and/or stabilization processing is generally performed. The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture and Television Engineers).
nalor the 5ociety of Moti
on Picture and Ta1evi-sio
n Engineers) Volume 64, p, 248-25
3 (May 1955 issue). Generally, the number of stages in the multistage countercurrent 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, from 0.52 to tj per 1 photosensitive material! Although the following is possible and the effects of the present invention are remarkable, problems such as increased residence time of water in the tank cause bacteria to propagate and generated floating matter to adhere to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very blindly. Also, JP-A-57-8
Isothiazolone compounds and thiabendazoles described in No. 542, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, JP-A No. 61-12014
Benzotriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal J (1986)
Sankyo Publishing, Hygiene Technology complete volume "Sterilization, sterilization, and anti-mildew technology of microorganisms" (1982) Industrial Technology Center, Japanese Society of Anti-Bacterial and Anti-Mold TL
It is also possible to use the disinfectants described in "Encyclopedia of Antibacterial and Mildew Resistant Agents J (1986)." Furthermore, in the washing water, surfactants can be used as draining agents, and chelating agents such as EDTA can be used as water softeners. It is possible to use a stabilizing solution following the above-mentioned water-washing step, or to directly process the stabilizing solution without going through the water-washing step.A compound having an image stabilizing function is added to the stabilizing solution, such as formalin. Typical aldehyde compounds and membrane p suitable for dye stabilization
Buffers for preparing l+ and ammonium compounds can be mentioned. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used. Furthermore, surfactants, optical brighteners, and hardeners may be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step, JP-A-57-
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used. In addition, it is also preferable to use chelating agents such as 1-hydroxyethylidene-1,1,-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds. A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the derailment process. The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45 degrees.
C. Preferably, the temperature is 20 to 40°C. The 0 time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing processing time.
Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to
The smaller the amount of replenishment in 1 minute and 30 seconds, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc. Example 1 32 g of lime-treated gelatin was added to 1000 cc of distilled water and dissolved at 40°C, then 3.3 g of sodium chloride was added and the temperature was raised to 60°C. Add N to this solution, N=-
1.8 cc of dimethylimidazolidine-2-thione (1% aqueous solution) was added. Next, a solution of 32-0 g of silver nitrate dissolved in 200 cc of distilled water and 11.0 g of sodium chloride were added.
A solution prepared by dissolving 200 cc of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 60°C. Further, a solution in which 128.0 g of silver nitrate was dissolved in 560 cc of distilled water and a solution in which 4 tons of sodium chloride and Og were dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 60°C. After desalting and washing with water at 40°C, 90.0 g of lime-treated gelatin was added, and the pAg was adjusted to 7.5 with sodium chloride and sodium hydroxide, and the pH was adjusted to 6.2.
Adjusted to. Subsequently, a red-sensitive sensitizing dye (S-1) was added at 8×10 −' mol per mol of silver halide, and sulfur sensitization was optimally performed at 50° C. using triethylthiourea. The silver chloride emulsion thus obtained was designated as Emulsion A. A silver chloride emulsion was prepared which differed from Emulsion A in that the pH was adjusted to 7.2 before sulfur sensitization and sensitization was optimized, and this was designated as Emulsion B. Emulsion A is a silver bromide ultrafine grain emulsion (grain size 0.05 μm) prepared at 50°C before sulfur sensitization.
．． After adding an amount containing 8 mol % of silver bromide and aging for 15 minutes, a silver chlorobromide emulsion was prepared which differed only in that sensitization was optimized, and this was designated as Emulsion C. A silver chlorobromide emulsion was prepared which differed from Emulsion C only in that the pH was adjusted to 6.7° before the addition of ultrafine silver bromide particles and sensitization was optimized, and this was used as an emulsion. A silver chlorobromide emulsion was prepared which differed from the emulsion in that the pH was adjusted to 7.degree.2 before the addition of ultrafine silver bromide particles and sensitization was optimized, and this was designated as Emulsion E. A silver chlorobromide emulsion was prepared which differed from Emulsion E in that the pH was adjusted to 7.8° before the addition of ultrafine silver bromide grains and sensitization was optimized, and this was designated as Emulsion F. Regarding the six types of emulsions A to F prepared in this way, the grain shape, grain size,
and particle size distribution was determined. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was calculated by dividing the standard deviation of the particle size by the average particle size. All six types of emulsions from A to F have a grain size of 0.
．． The particles were cubic particles with a diameter of 56 μm and a particle size distribution of 0.09. Electron micrographs of emulsions C, D, E, and F to which ultrafine silver bromide grains were added show that some of the cube corners are more pointed than those of emulsions A and B to which ultrafine silver bromide grains are not added. was doing. In addition, X-ray diffraction of Emulsions C, D, E, and F showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol % to 50 mol %. From the above, emulsions C, D, and E
It can be said that and F is obtained by epitaxially growing a localized phase having a silver bromide content of 10 mol % to 50 mol % in a corner part of cubic silver chloride grains. Red-sensitive sensitizing dye (S-1) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. 19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
Add and dissolve 8.2g of IV-1), and dilute this solution to 10%
1 containing 8 CC of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution. On the other hand, bulk silver bromide emulsion (cubic, 3-near mixture (silver molar ratio) with average grain size of 0.88 μm and 0.70 μm. The coefficient of variation of grain size distribution is 0.08 and 0.10, respectively. For large-sized emulsions, 2.0 x 10-4 mol of the blue-sensitive sensitizing dye shown below was added to each emulsion (containing 0.2 mol% silver bromide locally on the grain surface) per 1 mol of IL. For small size emulsions, 2.5X10'''
mol was added and then sulfur sensitized. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-) riazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer (2.0X1 G-' mole each for large-size emulsions and 2.5X1O-' mole each for small-size emulsions per mole of silver halide) Green-sensitive emulsion layer Red-sensitive emulsion The following compounds were added to the layer at 2.6XlO-' moles per mole of silver halide. (per mole of silver halide, 4.0 x 10'' moles for large size emulsions, 5.6 moles for small size emulsions)
X10-' mol) and 030 SOsll-N(CJs)3 (7.0X10-' mol for large size emulsions and 1.0X10-' mol for small size emulsions per mole of am halide) In addition, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, l-(5-methylureidophenyl)-5-mercaptotetrazole was added in grams per mole of silver halide.
, 5X 10-'mol, ? , 7XlG-'mol, 2.
5XlO-' moles were added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added per mole of silver halide to lXl0-'
mol and 2XIO-' mol were added. The following dyes were added to the emulsion layer to prevent irradiation. and s O, N9 (layer structure), the composition of each layer is shown below, the numbers are coating Il (g/rd
) represents the silver halide emulsion coating amount in terms of silver. Support polyethylene laminate paper [The polyethylene on the first layer side contains a white colorant (TIOI) and a blue dye (ulmarine blue)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 color image stabilizer (Cpd-
1) 0.19 solvent (Solv-1)
0.35 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv
-1) 0.16 solvent (Solv-4)
0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55 μm
A l:3 mixture of 0.39 μm and 0.39 μm (Ag
molar ratio) 0 The coefficient of variation of the particle size distribution is 0.10 and 0.
08, each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (C
pd-2) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (Cp d-
4) 0. 02 color image stabilizer (Cpd-9)
0.02 Solvent (Solv-2) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Fifth layer (red-sensitive layer) Silver chloride Emulsion A Gelatin Cyan coupler (ExC) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Solvent (Solv-6) Sixth layer (ultraviolet absorbing layer) Gelatin Ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (3o1v-5) Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
0.17 liquid paraffin
1: (Ex C) 1 mixture (molar ratio) of 0.03 (Ex A mixture of R''Cu1ls and CaH* (Cpd-3) color image stabilizer in a ratio of 2:4:4 by weight (Cpd-4) Color image stabilizer (Cpd-1) Color image stabilizer 0tNa (Cpd -5) Color mixture prevention agent (Cpd-2) Color image stabilizer H COOCglls (Cpd-6) Color image stabilizer (Cpd-8) Color image stabilizer c4u, (t) C*l1v (t) (Cpd-9 ) Color image stabilizer C4Hv(t) 2:4:4 mixture (weight ratio) of CH3CH2\/I (Cpd-7) Color image stabilizer+Cl1t Cll→1 Hs CH. CONHCJw(t) Average molecular weight 60° 00 (UV-1) Ultraviolet absorber H CsHz(t) HC41Lg(t) 11 C4H*(L) 4:2:4 mixture (weight ratio) (S, olv- 1) Solvent (Solv 5) Solvent C00CsHt? (CHx)s C00CsH+t (Solv-2) 2:1 mixture of solvent (volume ratio) (Solv-4) solvent The photosensitive material obtained in the above manner is referred to as A. Light-sensitive material A was prepared by replacing only the emulsion of the fifth layer (red-sensitive layer) as shown in Table 1, and these were designated as light-sensitive materials B, C%D, E, and F. In order to examine the sensitivity and gradation of the six types of photosensitive materials obtained in this way, they were exposed to light for 0.1 seconds through an optical wedge and a red filter, and after 1 hour, they were subjected to color development using the processing steps and processing solutions shown below. I did this. To investigate the safelight safety of photosensitive materials, we used Fujifilm's Safelight Filter 10 for color photographic paper.
The photosensitive material was exposed for 10 minutes through a 3A tungsten lamp at a distance of 1 m from an IOW tungsten lamp, followed by a 0.1 second wedge exposure and the same processing as above. In order to investigate the latent image stability of a photosensitive material, 0. Seventy-two hours after applying a 1 second wedge exposure, the same treatment as above was performed. Processing process Temperature Time Color development 35℃ 45 seconds bleach fixing
30-35℃ 45 seconds rinse 0 30-35
℃ Rinse for 20 seconds ■ 30-35℃
Rinse for 20 seconds ■ Dry for 20 seconds at 30-35°C Dry for 60 seconds at 70-80°C The composition of the treatment solution is as follows. Zuo Meng Eryi l blood water ethylenediamine-N,N. 00- N, N-tetramethylenephosphonic acid 1,5 g Potassium bromide triethanolamine Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate N, N-bis(carboxymethyl)hydrazine optical brightener (Kayu TIX 4B. Add water to pH (25℃) 1 liter of water Ammonium thiosulfate (70%) Sodium sulfite ethylenediaminetetraacetate iron (m) Ammonium 0 .015g 8,0g 1,4g 5g 5,0g 5,5g 1000w11 to, os 40(ld 100-7g 5g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water
1000 id pH (25℃) 6.0 ml ion exchange water (calcium, magnesium 3p9 each)
(below steel) Measure the reflection density of the treated sample prepared in this way,
The characteristic curve was obtained. The sensitivity (S) is 0.
5 is the reciprocal of the exposure amount required to provide a high density, expressed as a relative value with the sensitivity of photosensitive material A set as 100. Floor 11 (G
) is 0.0 at 1 ogE from the exposure amount for which the sensitivity was determined. 5 Expressed as the difference between the density for the increased exposure amount and the density for which the sensitivity was determined. As an evaluation of safelight safety, the density change ΔD (S) when irradiated with safelight was read at the exposure amount that gave a density of 0.5 to a sample that was not irradiated with safelight. As an evaluation of latent image stability, a sample processed after 1 hour of exposure was given a density of 0. The density change ΔD (L) in the case of processing after 72 hours of exposure at an exposure dose of 5 was read. These results are shown in Table 1. As is clear from the results in Table 1, emulsions A and B, which have a high silver bromide content and do not have a localized phase, have excellent safelight safety and latent image storage stability, but have low sensitivity and soft tone. Further, even if the pH during chemical sensitization is set high, there is only a slight change. Emulsion C, which has a localized phase with a high silver bromide content, has higher sensitivity than emulsion A, but is significantly inferior in safelight safety and latent image storage. Emulsions E and F, in which a localized phase with a high silver bromide content was formed and the surface was chemically sensitized at a relatively high pH, had dramatically improved safelight safety and latent image storage stability. Furthermore, higher sensitivity and higher contrast were achieved. A dramatic improvement in latent image storage stability according to the present invention was confirmed in the above emulsion in which fine silver bromide particles were added and the temperature during sulfur sensitization was changed to 56°C. Example 2 32 g of lime-treated gelatin was added to 1000 cc of distilled water, dissolved at 40°C, 3.3 g of sodium chloride was added, the pI was set to 6°2 with sodium hydroxide, and the temperature was lowered. The temperature was raised to 50°C.N, N--
2.7 cc of dimethylimidazolidine-2-thione (1% aqueous solution) was added. Next, a solution of 32.0 g of silver nitrate dissolved in 200 cc of distilled water and 11.0 g of sodium chloride were added.
A solution obtained by dissolving 100% of the above-mentioned product in 200 cc of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 50°C. Furthermore, a solution of 1.6 g of silver nitrate dissolved in 60 cc of distilled water and a solution of 1-12 g of potassium bromide dissolved in 60 cc of distilled water were added to
The mixture was added and mixed for 10 minutes while maintaining the temperature at 0°C. Furthermore, a solution in which 12 L of silver nitrate and Og were dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride was dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 50°C. Subsequently, a red-sensitive sensitizing dye (S-1) was added in an amount of 8×10 −S mol per mol of silver halide. After desalting and washing at 40°C, lime-treated gelatin 90-
After adding Og, the pAg was adjusted to 7.5 and the pH to 6.2 with sodium chloride and sodium hydroxide. Thereafter, sulfur sensitization was optimally performed using triethylthiourea at 50'C. The silver chlorobromide emulsion thus obtained (containing 1 mol % of silver bromide) was designated as Emulsion G. A silver chlorobromide emulsion was prepared that differed from Emulsion G only in that the pH was adjusted to 7.2 before sulfur sensitization and sensitization was optimized.
This was designated as Emulsion H. Add 32 g of lime-treated gelatin to 1000 cc of distilled water, dissolve at 40°C, add 3.3 g of sodium chloride, set the pH to 6°2 with sodium hydroxide, and raise the temperature to 50°C. I let it happen. Add 2 N,N-dimethylimidazolidine-2-thione (1% aqueous solution) to this solution.
-7cc was added. Next, add 32.0g of silver nitrate to 22.0g of distilled water.
A solution obtained by dissolving 11.0 g of sodium chloride in 200 cc of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 50°C. Further, a solution in which 128.0 g of silver nitrate was dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride was dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 50°C. Subsequently, the red-sensitive sensitizing dye (S-1) was added to silver halide.
8 x 10-5 moles were added per mole. Further, a solution in which 1.6 g of silver nitrate was dissolved in 60 cc of distilled water and a solution in which 1.12 g of potassium bromide was dissolved in 60 cc of distilled water were added and mixed over 10 minutes while maintaining the temperature at 50°C. After desalting and washing with water at 40°C, 90-0 g of lime-treated gelatin was added, and the pAg was adjusted to 7.5 and the pH to 6.2 with sodium chloride and sodium hydroxide. Thereafter, sulfur sensitization was optimally performed using triethylthiourea at 50°C. The silver chlorobromide emulsion thus obtained (containing 1 mol % of silver bromide) was designated as emulsion (2). A silver chlorobromide emulsion was prepared that differed from Emulsion I only in that the pH was adjusted to 7.2 before sulfur sensitization and sensitization was optimized.
This was designated as Emulsion J. Add 32 g of lime-treated gelatin to 1000 cc of distilled water, dissolve at 40°C, add 3.3 g of sodium chloride, set the pH to 6°2 with sodium hydroxide, and raise the temperature to 50°C. I let it happen. 2. N,N--dimethylimidazolidine-2thione (1% aqueous solution) was added to this solution.
7 cc was added. Next, a solution of 32-Og silver nitrate dissolved in 200 cc of distilled water and 11-0g of sodium chloride were added.
A solution obtained by dissolving 200 cc of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 50°C. Further, a solution in which 12 L Og of silver nitrate was dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride was dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 50°C. Subsequently, a red-sensitive sensitizing dye (S-1) was added in an amount of 8.times.10@-' moles per mole of silver halide. A silver bromide ultrafine grain emulsion (grain size 0.05 μm) was added in an amount containing 1.0 mol% silver bromide based on silver chloride, and 15
After aging for a minute, desalting at 40°C and washing with water, 90.0 g of lime-treated gelatin was added, and sodium chloride and sodium hydroxide were added to i) Ag to 7.5.
The pH was adjusted to 6.2. Thereafter, sulfur sensitization was optimally performed using triethylthiourea at 50°C. Silver chlorobromide emulsion thus obtained (containing 1 mol% silver bromide)
was made into an emulsion. A silver chlorobromide emulsion was prepared that differed from the emulsion in that the pH was adjusted to 7.2 before sulfur sensitization and sensitization was optimized.
This was made into an emulsion. The six types of emulsions from G to L all have a grain size of 0.
．． The particles were cubic particles with a diameter of 50 μm and a particle size distribution of 0.11. Electron micrographs of Emulsions 1, J, 2, and L showed that some of the cube corners were more pointed than those of Emulsions G and H. In addition, X-ray diffraction of emulsions G, H11, J, and L shows that the silver bromide content ranges from 10 mol% to 50 mol%.
A considerable portion of the sample showed weak diffraction. From the above, emulsions G and H contain a localized phase with a silver bromide content of 10 mol% to 50 mol% inside the grains, and emulsions ①, J, and L
The silver bromide content is 1 in some corners of the cubic silver chloride grains.
It can be said that 0 mol % to 50 mol % of the localized phase is epitaxially grown. The photosensitive material A of Example 1 is a photosensitive material in which only the emulsion in the fifth layer (red-sensitive layer) is replaced as shown in Table 2, and these are added to photosensitive materials G, H1, J, and L. And so. The sensitivity, gradation, safelight safety, and latent image stability of the six kinds of light-sensitive materials thus obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2. As is clear from the results in Table 2, when comparing emulsions G and H, which contain localized phases with high silver bromide content inside the grains,
The effect of pH during chemical sensitization on sensitivity, gradation, safelight safety and latent image storage stability is very small. Comparing Emulsion ■ with localized phases with high silver bromide content near the grain surface, Emulsions J and L, which were chemically sensitized at a relatively high pH, have good safelight safety and The storage stability of latent images has been dramatically improved, and higher sensitivity and higher contrast have been achieved. Furthermore, the effect is remarkable in emulsions in which ultrafine silver bromide grains are added to form localized phases with a high silver bromide content near the grain surfaces. Example 3 32 g of lime-treated gelatin was added to 1000 cc of distilled water and dissolved at 40°C, then 1.6 g of sodium chloride was added and the temperature was raised to 54°C. In this solution, N, N--
1.7 cc of dimethylimidazolidine-2-thione (1% aqueous solution) was added. Next, a solution of 32.0 g of silver nitrate dissolved in 200 cc of distilled water and 11.0 g of sodium chloride were added.
A solution prepared by dissolving 200 cc of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 54°C. Further, a solution in which 128.0 g of silver nitrate was dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride was dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 54°C. After desalting and washing with water at 40°C, 90-Og of lime-treated gelatin was added, and the pAg was adjusted to 8°1 and the pH was adjusted to 6° with sodium chloride and sodium hydroxide.
．． Adjusted to 0. After raising the temperature to 46 DEG C., 6.times.10@-5 moles of red-sensitive sensitizing dye (S-1) were added per mole of silver halide. Next, silver bromide ultrafine grain emulsion (grain size 0
．． 05 μm) was added in an amount containing 0.55 mol % of silver bromide based on silver chloride, and after ripening for 25 minutes, sulfur sensitization was optimally performed at 46° C. using triethylthiourea. The silver chlorobromide emulsion thus obtained (silver bromide was added to 0.5
5 mol %) was designated as Emulsion M. Emulsion M is a silver chlorobromide emulsion that differs only in that the sensitization is optimized after the ultrafine silver bromide grain emulsion is added and heated, and the pH is adjusted to 7.3 with sodium hydroxide before sulfur sensitization. Prepare,
This was designated as Emulsion N. Emulsion M was prepared by adjusting the pH to 7.3 with sodium hydroxide before adding the silver bromide ultrafine grain emulsion, and then adjusting the pH to 6.3 with sulfuric acid just before starting sulfur sensitization. After adjusting the emulsion to 0, a silver chlorobromide emulsion was prepared which differed only in that the sensitization was optimized, and this was designated as emulsion O. A silver chlorobromide emulsion was prepared that differed from Emulsion M in that the pH was adjusted to 7.3 with sodium hydroxide before addition of the silver bromide ultrafine grain emulsion to optimize sensitization. And so. Emulsion M is a silver bromide ultrafine grain emulsion that is added before sulfur sensitization and contains 1.1 x 10-5 mol of potassium hexachloroiridate (IV) per 1 mol of silver bromide in advance to optimize sensitization. A silver chlorobromide emulsion was prepared which differed only in that the emulsion was converted into an emulsion. Emulsion P is a silver bromide ultrafine grain emulsion that is added before sulfur sensitization by adding 1.1 x 10-5 mol of potassium hexacrotoiridate (IV) per 1 mol of silver bromide, and sensitizing it. A silver chlorobromide emulsion was prepared which differed only in that it was optimized, and this was designated as emulsion R. All six types of emulsions from M to R have a grain size of 0.
．． The particles were cubic particles with a diameter of 52 μm and a particle size distribution of 0.10. The electron micrographs of emulsions M, N, O, P, Q and R are
Some of the corners of the cube had a sharp shape. Further, X-ray diffraction of these emulsions showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol % to 50 mol %. From the above, it can be said that these emulsions have a localized phase having a silver bromide content of 10 mol % to 50 mol % epitaxially grown on a part of the corner of cubic silver chloride grains. The photosensitive material A of Example 1 is a photosensitive material in which only the emulsion in the fifth layer (red-sensitive layer) is replaced as shown in Table 3, and these are combined with photosensitive materials M, N, O, P, Q and It was set as R. The sensitivity, gradation, safelight safety, and latent image stability of the six kinds of light-sensitive materials thus obtained were evaluated in the same manner as in Example 1. The results are shown in Table 3. As is clear from the results in Table 3, ripening in an atmosphere with a pH of 6.5 or higher is carried out only when a localized phase with a high silver bromide content is formed, or only when the surface is chemically sensitized. Although the effects of the present invention can be obtained even if the pH is 6.
Particularly remarkable effects can be obtained by maintaining the atmosphere in an atmosphere of 5 or more. In addition, by forming a localized phase with a high silver bromide content in the presence of an iridium compound, an emulsion with high contrast can be obtained even in high-intensity exposure as in this experiment, but safelight safety is significantly deteriorated. . In the emulsion R of the present invention containing an iridium compound,
It can be seen that the effects of the present invention are remarkable. (Effects of the Invention) The present invention is suitable for rapid processing, has high sensitivity, high contrast,
Moreover, it is possible to obtain a silver halide photographic light-sensitive material which has excellent safelight safety and also has good latent image storage properties over a long period of time.

Claims (4)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive emulsion layer on a support, the silver halide emulsion contained in the emulsion layer is present near the surface of the silver halide grains with a silver bromide content of at least After forming a localized phase of more than 10 mol %, the surface is chemically sensitized to obtain a silver chlorobromide emulsion in which 95 mol % or more is silver chloride, which is substantially free of silver iodide, and A silver halide photographic light-sensitive material characterized in that it is an emulsion that has been aged in an atmosphere with a pH of 6.5 or higher from the start of local phase formation to the end of surface chemical sensitization. (2) Formation of the localized phase is achieved by mixing silver halide fine grains with a smaller average grain size than the silver halide host grains and with a higher silver bromide content in the cubic or tetradecahedral silver halide host grains. Claim No. 1 (1) is an emulsion produced by ripening and ripening.
) The silver halide photographic material described in item 1. (3) The silver halide according to claim (1) or (2), wherein the emulsion is one in which the localized phase is formed in the presence of an iridium compound. Photographic material. (4) Claims characterized in that the emulsion is aged in an atmosphere with a pH of 7.0 or more and 7.7 or less between the start of formation of the localized phase and the end of chemical sensitization of the surface. The silver halide photographic material according to item (1), item (2), or item (3).