JPH02217840A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress the generation of fogging while maintaining characteristics, such as high sensitivity and higher contrast, by using a silver chlorobromide emulsion obtd. by chemically sensitizing the silver chlorobromide particles subjected to a halogen conversion treatment on the surface under a prescribed alkaline condition in the presence of nucleic acid. CONSTITUTION:The silver halide particles which consist of the silver chlorobromide contg. substantially no silver iodide and having the plural partial structures varying in halogen compsn. are subjected to the halogen conversion on the surface and are chemically sensitized in a 7.0 to 9.0 pH range in the coexistence of the nucleic acid or the decomposition product thereof after a desalting treatment to obtain the silver chlorobromide emulsion. This emulsion is incorporated into at least one of the emulsion layers on a base. The high sensitivity and the high contrast are obtd. in this way and the fogging at the time of development is suppressed.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic material having high sensitivity, high contrast, and low fogging during development. This invention relates to a silver halide photographic material in which generation is suppressed.

(Prior Art) In silver halide photosensitive materials, especially photosensitive materials for printing, in recent years there has been a strong demand for higher sensitivity and faster development processing, and over the past 50s, technological developments have been made to shorten the process. They have been developed one after another and introduced into the market. An example of such technology is increasing the sensitivity of photosensitive materials (reducing printing time).

Techniques for improving the development speed (shortening the development process) can be cited.

In order to increase the sensitivity of a silver halide emulsion, there are two methods: increasing the amount of light absorbed per silver halide grain, and increasing the efficiency of forming a latent image with respect to the amount of absorbed light.

For the former, the size of the silver halide grains can be increased to increase the amount of light absorbed per grain, or if the emulsion is spectrally sensitized, the amount of spectral sensitizing dye can be increased. One possibility is to increase the amount of light absorption. However, it is known that when the size of silver halide grains is increased, the development speed often decreases. Furthermore, it is known that increasing the amount of spectral sensitizing dye inhibits development or desilvering. Therefore, these methods often have problems when put into practical use.

As for the inner layer, it is effective to apply a method known as so-called chemical sensitization, such as sulfur sensitization, gold sensitization, or reduction sensitization, either alone or in combination. however,
There are limits to the sensitivity that can be achieved with these methods as well. That is, excessive chemical sensitization often causes an increase in fog and a decrease in contrast when exposed to high illumination for a short time.

Therefore, it is an important issue to increase the sensitivity of emulsions while keeping the size of silver halide grains constant and without causing the above-mentioned disadvantages.

On the other hand, regarding the improvement of the development speed of silver halide emulsions,
It is known that increasing the silver chloride content or using pure silver chloride is effective for reducing the size of silver halide grains or for silver chlorobromide that does not substantially contain silver iodide. . However, when these methods are used, the amount of light absorbed per silver halide grain decreases, which leads to a decrease in sensitivity in conventional methods. Increasing the sensitivity of emulsions is an important issue.

As an example of a method for obtaining a highly sensitive silver halide emulsion, a method for forming emulsion grains by halogen conversion is disclosed in Japanese Patent Publication No. 50-369.
It is disclosed in No. 78. However, it has been found that although the emulsion obtained by this method exhibits increased sensitivity, it suffers from significant desensitization when pressure is applied to the light-sensitive material, and the obtained gradations also become soft.

In addition, as a method for obtaining a silver halide emulsion with high sensitivity and improved development speed, several examples of laminated emulsions having layers with different halogen compositions inside silver halide grains have been disclosed.

For example, Japanese Patent Publication No. 56-18939 describes an emulsion produced by coating a silver bromide core with silver chloride or depositing a layer of silver bromide on a silver chloride core, which combines the advantages of both. There is a statement to that effect. However, the technique disclosed herein is coated with different silver halide layers.
According to the test results of the present inventors, eight examples in which emulsions with favorable performance were not necessarily obtained were listed as follows: Emulsions prepared according to the above techniques tend to produce reversed images from relatively low exposure ranges;
Further, they often had drawbacks such as large desensitization when pressure was applied to the emulsion. Furthermore, the obtained gradation is often soft, and in particular, the legs of the characteristic curve are sometimes soft and have two levels of gradation.

Furthermore, in JP-A No. 58-9137, a laminated silver chloroiodobromide emulsion having 50 mol% or more of silver bromide in the outermost layer is chemically sensitized with an unstable sulfur compound in the presence of fine grain silver chloride. The technology to do so is described. However, when we tried to prepare a layered emulsion according to the technique disclosed herein, we found that the leg gradations of the characteristic curve tended to soften, and that desensitization was likely to occur when pressure was applied. It was done.

Furthermore, it has been reported that a technique for forming a layered structure is effective in increasing the sensitivity of silver chlorobromide emulsions having a high silver chloride content.

For example, JP-A-58-95736 and JP-A-58-10
No. 8533 discloses a technique relating to a high silver chloride emulsion having a layered structure. According to the former, by having a layer mainly composed of silver bromide inside the 4 grains,
It is said that rapid processing is possible and emulsions with high sensitivity can be obtained, but in actual tests, it was found that desensitization easily occurs when pressure is applied to emulsion grains, making it difficult to put it to practical use. was discovered. According to the latter, by localizing a layer mainly composed of silver bromide on the grain surface, it is possible to obtain an emulsion that can be processed quickly, has high sensitivity, and has a wide chemical sensitization latitude. but,
When actually tested, it was found that this also has the disadvantage that the legs of the characteristic curve tend to soften, in extreme cases it shows two-step gradation, and it tends to cause desensitization due to pressure. Ta.

In addition to these, JP-A-60-222844 and JP-A-60-222844
No. 0-222845 also discloses a technique regarding a highly basic silver emulsion provided with a layered structure. however,
Even if these techniques are followed, the above-mentioned drawbacks have not been resolved.

Furthermore, JP-A No. 63-28273 discloses that the surface of silver halide grains, which are made of silver chlorobromide substantially free of silver iodide and have a plurality of layers with different halogen compositions inside the grains, is converted to halogen. It is described that by using a surface temperature image type monodisperse silver chlorobromide emulsion obtained by this method, high sensitivity and high tone tones can be obtained, and desensitization due to pressure can be reduced.

With this technique, pressure desensitization is significantly improved.

However, in practical systems, high sensitivity, high contrast, and fog during chemical sensitization are still insufficient (further improvements in these points are required).

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity and high contrast and suppresses fogging during development.

(Means for Solving the Problems) As a result of intensive research to overcome the drawbacks of such conventional silver halide photosensitive materials, the present inventors have developed a silver halide photosensitive material having a plurality of different partial structures, High sensitivity, high contrast (high contrast), etc. can be achieved by using a silver chlorobromide emulsion obtained by chemically sensitizing silver chlorobromide grains whose surfaces have been subjected to halogen conversion treatment under specified alkaline conditions in the presence of nucleic acids. The inventors have discovered that it is possible to achieve the objective of suppressing the occurrence of fog while maintaining the characteristics of the invention, and based on this knowledge, the present invention has been completed.

In other words, the present invention converts silver halide grains, which are made of silver chlorobromide substantially free of silver monoiodide and has a plurality of partial structures having different halogen compositions, into halogens on the surface and after desalting treatment. , at least one emulsion layer on the support contains a silver chlorobromide emulsion obtained by chemical sensitization in the pH range of 7.0 to 9.0 in the coexistence of a nucleic acid or its decomposition product. The present invention provides a silver halide photographic material having the following properties.

Hereinafter, the content of the present invention will be explained in detail.

A useful silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide containing substantially no silver iodide. "Substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.
．． The content ratio of silver dichloride and silver bromide in the emulsion used in the present invention ranges from close to pure silver chloride to pure silver bromide. It is preferable that the silver bromide content is 0.3 mol% or more and 97 mol% or less.

In order to obtain a photographic material with stable fog, sensitivity, and gradation using the technology of the present invention, it is desirable to have a high silver bromide content in the emulsion, preferably 45 mol% or more of silver bromide, Further, it is preferably 60 mol% or more.

In such a silver chlorobromide emulsion of the present invention, it is necessary that the crystal grains contained therein have at least two partial structures having silver bromide contents different by 10 mol% or more. The partial structure referred to herein may have a so-called core-shell type structure in which the inside and surface of the crystal grain differ in halogen composition, or may further have a plurality of layered structures. Note that the layer structure referred to here is not necessarily continuous, and may have a discontinuous layer structure such as epitaxial growth on a corner or surface.

Silver halide grains having such a plurality of partial structures can be prepared by, for example, the method described in JP-A-63-282730.

In the partial structure formed in this way, for example, in a crystal grain with a core-shell structure, the core part has a high silver bromide content and the shell part has a low silver bromide content (although the reverse is also possible). In addition, even if the boundaries between substructures of crystal grains having these structures with different halogen compositions are clear boundaries in terms of composition, they may form mixed crystals due to one difference in composition and change continuously. There may be.

There is no particular restriction on the composition ratio of two or more partial structures with different halogen compositions in a crystal grain, but for example, in a crystal grain with a core-shell structure, the molar ratio of the constituent silver halide between the core and the shell is 2:98 to 98. : The ratio of core to shell is preferably between 2 and more preferably 10:9.
It is between 0 and 95:5, more preferably 40:
It is between 60 and 90:1O. Most preferably 67:3
It is between 3 and 90:10.

The difference in silver bromide content between the core part and the shell part varies depending on the constituent molar ratio of the core part and the shell part, but it needs to be at least 10 mol% or more and less than 100 mol%. Preferably it is 10 mol% or more and 50 mol% or less. Most preferably it is 15 mol% or more and 35 mol% or less. If the silver bromide content differs very little between two or more partial structures, it will not be much different from grains with a uniform structure; on the other hand, if the composition difference is too large, performance problems such as pressure desensitization may occur. This is not desirable as it can easily cause this. The appropriate compositional difference depends on the compositional ratio of the partial structure, and it is preferable that the compositional difference be larger as the compositional ratio approaches O:100 or 1002O.
:l, the compositional difference is preferably reduced to a certain range of 10 mol% or more.

The term "halogen conversion" used in the present invention means "
It is defined as "changing the composition of already formed silver halide crystals by adding a substance containing halogen ions that can form a less soluble silver salt." A typical example of this is the reaction in which silver chloride is converted to silver bromide, which occurs when potassium bromide is added to a pure silver chloride emulsion, but in general, silver chloride undergoes halogen conversion. This occurs when the silver halide crystal is a mixed crystal such as silver chlorobromide and an amount of bromide ion is introduced into the solution that exceeds the concentration of bromide ion present in the solution in equilibrium with the silver halide crystal. This usually includes reactions in which silver halide is converted into a composition richer in silver bromide.

Next, to halogen-convert the surface of such particles,
Although it is convenient to add the required amount of bromide ion as a water-soluble bromide, it is also possible to use a donor in which the amount or rate of bromide ion supplied can be controlled. These include:
Organic bromides, inorganic bromides with moderate solubility in water, bromides covered with capsule membranes or semi-permeable coatings, etc. can be used. Furthermore, it is also possible to use fine-grain silver halide having a silver bromide content higher than that of the silver bromide content on the grain surface before halogen conversion.

In the present invention, the amount of halogen conversion is preferably 0.5 mol% or more and 20 mol% or less based on the total silver halide,
Furthermore, it is preferably 1 mol% or more and 15 mol% or less. If the amount is less than 0.5 mol, the effects of the present invention will not be readily apparent, and if it exceeds 20 mol %, the desensitization due to pressure described above will increase, which is not preferable.

As is generally well known, the preparation process of the silver halide emulsion in the present invention consists of a silver halide grain formation process by reaction of a water-soluble silver salt and a water-soluble halide, a desilvering process, and a chemical ripening process. In the present invention, the halogen conversion is preferably carried out before the chemical ripening step, more preferably before the desilvering step, and particularly preferably after grain formation. .

Nucleic acids used in the present invention include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), and nucleic acid decomposition products include those in the middle of decomposition and simple substances such as adenine, guanine, uracil, cytosine, and thymine. It will be done. Adenine is particularly preferred as a nucleic acid degradation product. These can be used alone or in combination. In this case, it goes without saying that a combination of a nucleic acid and a nucleic acid degradation product may be used. The amount of the nucleic acid or its decomposition product added varies depending on the type of the nucleic acid decomposition product, but is 20 mg per mole of the halogenated ml.
The above amount is preferably in the range of 100 mg to 1 g. As mentioned above, when these nucleic acids or nucleic acid degradation products are used alone or in combination of two or more, the above-mentioned total amount is sufficient.

In the present invention, the silver halide emulsion in the silver halide emulsion layer is chemically sensitized by allowing nucleic acids or decomposition products thereof to coexist before the end of chemical sensitization. In this case, it is preferable to carry out sulfur sensitization as the chemical sensitization, but reduction sensitization, gold sensitization, etc. may be used in combination.

The chemical sensitization treatment with sulfur used in the present invention is
This is carried out using active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfates, thioureas, mercap! compounds, and rhodanines), specific examples of which are described in U.S. Patent No. 1. ．． No. 574,944, No. 2,278,947
No. 2,410.689, No. 2,728,66
No. 8, No. 3,656,955, and other specifications.

In the chemical sensitization treatment in the present invention, the pH is adjusted to 760 to 9.0.
It is necessary to do so within the following range. pH is defined as the common logarithm of the reciprocal of the hydrogen ion concentration, and the method used to measure it is generally to measure the dynamic force of a battery that combines a glass electrode and a Cancora electrode. It can be easily measured using a pH meter.

It is generally known that the rate of progress of chemical sensitization changes depending on conditions such as temperature and pHlpAg. In particular, regarding pH, the rate of progress becomes faster when pi-+ is higher, that is, when the hydrogen ion concentration is higher, and It is said that fogging is likely to occur.

The pH range in the present invention is a relatively high range for chemical sensitization of silver chlorobromide emulsions (conventionally, the pH range was 5.5 to 6.5), and the conventional method did not solve the problem of increased fog. Although the conditions were difficult to overcome, high sensitivity and contrast could be obtained in the presence of silver chlorobromide particles and nucleic acids or decomposition products thereof according to the present invention. Especially with regard to this high contrast, this was an unexpected effect that could not be achieved by any of the other methods considered.

A more preferable pH range in the present invention is 7.0 to 8.
5, more preferably in the range of 7.3 to 8.0.

The silver chlorobromide emulsion grains used in the present invention have regular crystal shapes such as cubes and octahedrons, and those having irregular crystal shapes such as spherical and plate shapes. , or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide emulsion used in the present invention has a thickness of 0.5
It is a tabular grain emulsion in which grains having a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area. A monodisperse emulsion having the above coefficient of variation (value S/1 obtained by dividing the standard deviation S by the diameter 1 in a distribution expressed by a diameter when the projected area is approximated by a circle) of 20% or less is preferable. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is B. gelafchides (P
, Glafkides), “Chimfe et Physique Photographic J”
PhysiquePhoLggraphequel (
Paul Montell Publishing, 1967), G. F. Duffin, Photographic Emulsion Chemistry J.
graphic emulsion chemist
ry) (Focal Press, 1966), V.
Making and Coating Photographic Emulsions J, by El Zelikman (V, L, Zelikman) et al.
CoatingPhotographic Emul
sion) (Published by Focal Press, 1964)
It can be prepared using the method described in et al.

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. Nos. 3,271,157 and 3,574) are used as silver halide solvents to control grain growth. , No. 628, No. 3,704,130,
4.297.439, 4.276.374, etc.), thione compounds (for example, JP-A-53-14431)
No. 9, No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A No. 54-100717),
etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc 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, etc. may be present together.

Silver halide emulsions are usually spectrally sensitized. For spectral sensitization, ordinary methine dyes can be used, and the details thereof can be found in JP-A No. 62-215272, page 22, line 3 from the bottom of the upper right column to page 38, and March 16, 1988. It is stated in Appendix B of the procedural amendment.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole and its phenyl substituted products), mercaptopyrimidines; carboxyl group The above-mentioned heterocyclic mercapto compounds having water-soluble groups such as Many compounds known as antifoggants or stabilizers can be added, such as indenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like.

Specific examples of particularly preferred compounds are described on pages 40 to 2 of the specification of JP-A-62-215272.

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. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention have the following general formulas (1), (11), (III), (1v) and (
V).

General formula (I) General formula (II) General formula (III) General formula ([V) General formula (V) [However, in general formulas (I) and (II), R5, R
1 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, Rs and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R1 represents R2 and The co-number may represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring,
Y, , Y represents a hydrogen atom or a vine group that is separated during the coupling reaction with the oxidized product of the developing agent.] R6 in the general formula n) is preferably an aliphatic group, such as a methyl group. , ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, etc. can.

Preferred examples of the cyan coupler represented by the general formula (I) or (U) are as follows.

In general formula (I), R6 is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, More preferably, it is an aryl group substituted with a sulfamide group, an oxycarbonyl group, or a dicyano group.

In general formula (1), when R3 and R3 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R1 is preferably a hydrogen atom.

In general formula (II), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (II), R6 preferably has 2 to 15 carbon atoms.
It is a methyl group having an alkyl group and a substituent having one or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (II), 86 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (II), R6 is preferably a hydrogen atom or a halogen atom, with chlorine atom and fluorine atom being particularly preferred; Y in general formulas (1) and (II);
and Y2 are each a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group.

In the general formula (Ill), R7 and R9 represent an aryl group, R6 represents a hydrogen atom, an aliphatic or aromatic acyl group, 5 an aliphatic or aromatic sulfonyl group, and Y3 represents a hydrogen atom or a leaving group. IIR? The substituents allowed on the aryl group (preferably the phenyl group) of and R are the same as the substituents allowed on the substituent R3.

When there are two or more substituents, R1, which may be the same or different, is preferably a hydrogen atom, an aliphatic acyl group or a phenyl group, particularly preferably a hydrogen atom.

Preferred Yl is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, 1 e.g. U.S. Pat.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51.897 and Wo 88104795.

In the general formula (rv), 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.
, Z b and Zc represent methine, substituted methine=N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. Z
The case where the b-Zc bond is a carbon-carbon double bond includes the case where it is part of an aromatic ring. This includes the case where R2° or Y forms a dimer or more multimer, and when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (IV), imidazo[1,2-bl], which is described in U.S. Pat. Pyrazoles are preferred, including pyrazolo[1,5
-bl [1°2.4] Triazole is particularly preferred.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2,3 or 6 position of the pyrazolotriazole ring as described in JP-A No. 61-65245, and as described in JP-A-61-65246 pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having more alkoxyphenylsulfonamide ballast groups described in JP-A-61-147254, and European Patent Publication No. 226.849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in .

In the general formula (V), R1 represents a halogen atom or an alkoxy group, R11 represents a hydrogen atom, a halogen atom, or an alkoxy group, and A represents -NHCOR0, NH
S Ox RIx, -So, NHR,, -COOR
, 2, -5O, N-R+s, where R13 and R14 each represent an alkyl group, mY% represents a leaving group, R18, R13% R8 substituents include R1
The leaving group Y is preferably of the type leaving off at either an oxygen atom or a nitrogen atom, with the leaving group Y leaving at a nitrogen atom being particularly preferred.

Specific examples of couplers represented by general formulas (1) to (V) are listed below.

(C-/) (C-, z) (c-B (C-J) 2 (C-7) α (C-p) α (c-B α (C-t) (C-2) ( C-10) (i (C-/J) (Sushi6M13 (C-/7) (C-/, r) (C /2) (C-ip) (C-tr) (C-//;) (C-,20) OCH2CHC4H1 2H5 (C,2/ (C-,2,2> (M-g) (~[-j) α (M-,A) (M-7) α H3 a(3 ( Y-/) (Y-,2) (Y-4> α (Y-A) (Y-7) (Y-3) (Y-Hiroshi) (・Y-4) General formulas (1) to ( The coupler represented by V) is usually present in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 mol per mol of silver halide.
~0.5 mol is contained.

In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be applied.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 droplet dispersion in ice with phase inversion.
Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the galvanic rate (25℃)
It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 2 to 20, 1 and 3 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) General formula (B) W, -COO-Wz General formula (C) / W, -CON \ General formula (D) General formula (E) w, −0−W.

(In the formula, W+, W, and W each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, and W4 is W,, O
represents W or S-W, n is an integer from 1 to 5, and when n is 2 or more, W may be the same or different from each other, and in general formula (E), Wl and W , may form a condensed ring.) The high boiling point organic solvent used in the present invention has a melting point of 100°C or less and a boiling point of 140°C, even if other than general formula (A) or E).
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. The boiling point of the high boiling point organic 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-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be impregnated into rhodapulu latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling v1'rd media described above, or by impregnating water-insoluble and organic It can be dissolved in a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. N08g100723 are preferably used, and acrylamide-based polymers are preferably used from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as one-color antifoggants.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, organic antifading agents for cyan, magenta and/or yellow images include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Can be mentioned. Also, (bissalicylaldoximide)nickel complex and (bis-N).

Metal complexes such as N-dialkyldithiocarbamado) nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
2.418,613, 2.700.453, 2,701,197, 2,728,659
No. 2.73.2,300, No. 2,735.7
No. 65, No. 3.982.944, No. 4,430,
425, British Patent No. 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans are U.S. Patent No. 3°432.3
No. 00, No. 3,573,050, No. 3,574,
No. 627, No. 3,698,909, No. 3,764
．． No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360,589, p.
-Alkoxyphenols are U.S. Patent No. 2,735,7
No. 65, British Patent No. 2,066.975, JP-A-59
-10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3,700,455.
No. 52-72224, U.S. Patent No. 4,228
, 235, and Japanese Patent Publication No. 52-6623, and gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3,457,079, U.S. Pat. -21144 etc., hindered amines are disclosed in U.S. Patent No. 3゜336.13.
No. 5, No. 4,268,593, British patent cylinder 1.32
．． No. 889, No. 1.354.313, No. 1, 4
No. 10,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983
-114036, 59-53846, 59-7
No. 8344, etc.; metal complexes are disclosed in U.S. Pat. No. 4,050,
No. 938, No. 4,241,155, British Patent No. 2.
No. 027,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. 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 the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,79
4), 4-deazolidone compounds (e.g., U.S. Pat. No. 3,314°794, U.S. Pat. No. 3,352,6)
81), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805,
No. 3,707,375), butadiene compounds (e.g., as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., as described in U.S. Pat. No. 3,700,455). ) can be used. UV-absorbing couplers (e.g. a-
Naphthol-based cyan dye-forming couplers), ultraviolet absorbing polymers, etc. may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) 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 aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. 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 color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant with p-anisidine of 2 (in trioctyl phosphate at 80°C) of 1. Ofl/molsec-I
It is a compound that reacts in the range of O''''12/a+ol -5ec. Note that the second-order reaction rate constant is based on JP-A-63
It can be measured by the method described in No.-158545.

When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (FI) or (FU).

General formula (FI) R, -(A). -X General formula (FII) R, -C=Y In the formula, R, and R each represent an aliphatic group, an aromatic group, or a heterocyclic group, n represents 1 or O, and A is an aromatic group. X represents a group that reacts with a group amine developer to form a chemical bond, and X represents a group that reacts with an aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y
represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fll). R+ here
and X%Y and R2 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.

For specific examples of compounds represented by general formulas (Fl) and (Fil), see JP-A-63-158545 and JP-A-62-
Preferably, those described in specifications such as No. 283338, Japanese Patent Application No. 158342/1983, and European Patent Publication No. 277589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inactive and colorless compound is the following general formula (Gl ).

General Formula (G1) In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z represents Pearson's nucleophilic group 'C) In I
Value (R,G, Pearson, et al.

J, Arm, Cheffl, Soc, 90.
319 (1968)) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, No. 62-1583
Preferred are those described in No. 42, European Patent Publication No. 277589, and the like.

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 may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include: Included are 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 advantageous 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 nitrace film and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used.6 For the purpose of the present invention, reflective supports are used. is more preferable.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support6. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide. Film, polycarbonate film, polystyrene film, vinyl chloride resin, 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 calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (R,). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio S/π of the standard rs deviation S of R to the average value (ball) of R+. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined by:

In the present invention, the variation coefficient of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles is substantially "uniform". It can be said that.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 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 their sulfates, hydrochlorides or p-toluenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, Auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'
-tetramethylenephosphonic acid, ethylene glycol (O
-hydroxyphenylacetic acid) and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but it is generally 312 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 500 or less.
It can also be lower than suri. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately, and in order to speed up the process, a bleach-fixing process may be performed after the bleaching process.
Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), cobalt (Ill),
Compounds of polyvalent metals such as chromium (vi) and copper (■), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (
■Organic complex salts of cobalt(III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
1. Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid; persulfates;
Bromate; permanganate; nitrobenzenes, etc. can be used. Among these, iron(III) aminopolycarboxylate complex salts and persulfates, including iron(III) i salt of ethylenediaminetetraacetate, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Complex salts are particularly useful in both bleach and bleach-fix solutions. pl (
is usually 565 to 8, but for faster processing, it is also possible to process at an even lower pH.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858;
, No. 290,812, JP-A-53-95630, Research Disclosure No. 17129 (197
Compounds having a mercapto group or disulfide bond as described in J. No. 1987 (July 1983); thiazolidine derivatives as described in JP-A No. 140129/1983; U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2,748.430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect.
In particular, US Patent No. 3,893,858, West German Patent No. 1.
Preferably, the compounds described in No. 290.812 and JP-A-53-95630, and also US Pat. No. 4,552.83
The compounds described in No. 4 are also preferred. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Thiosulfate and thiocyanate are used as fixing agents.

Examples include thioether compounds, thioureas, large amounts of iodide salts, etc., but thiosulfates are commonly used, and ammonium thiosulfate can be used most widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

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 application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as alternating current or forward flow, and various other conditions. Can be set to . this house,
The relationship between the number of flushing tanks and the amount of water in the multi-stage AC system is as follows:
Journal of the 5ociety
of Motion Picture and
Te1evision Engineers Volume 64,
It can be determined by the method described in p., 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of washing water can be significantly reduced, but bacteria will grow due to the increased residence time of water in the tank.

In the processing of the color photosensitive material of the present invention, problems such as adhesion of generated suspended matter to the photosensitive material may occur.As a solution to such problems, calcium ions and magnesium ions as described in JP-A-62-288838 have been proposed. It is possible to use a method of reducing this extremely effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, ``Chemistry of antibacterial and antifungal'' by Hiroshi Horiguchi ( 1986) Sankyo Publishing,
Hygiene technology gold wire [sterilization of microorganisms, sterilization, anti-mildew technology J (
It is also possible to use the fungicides described in the Society of Industrial Science and Technology, Japan Antibacterial and Antifungal Society (1982), Dictionary of Antibacterial and Antifungal Agents J (1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The water washing temperature and water washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-14834
All known methods described in No. 60-220345 can be used.

Furthermore, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Ship base type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in '924, U.S. Patent No. 3.71
Metal complex described in No. 9,492, JP-A-53-13562
The urethane compounds described in No. 8 can be mentioned.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64339, JP-A-57-144547,
and No. 58-115438.

The various processing solutions used in the present invention are used at temperatures ranging from 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate the processing, shorten the processing time, or reverse This makes it possible to improve the image quality and the stability of the processing solution by lowering the temperature. Furthermore, for the purpose of recording photosensitive materials, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

(Example) The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these embodiments.

(Example 1) A silver chlorobromide emulsion (i) before chemical sensitization was prepared as follows.

(1 liquid) 2O NaCβ Br Gelatin (21ft) Compound below (1%) H3! a'(3 (3 liquids) Br NaCβ K a I r CI2(, (0,001%) H,O
(4 liquids) A g N O5 NH4NOs (50%) Add HaO 00cc 6,9g 0,4g 32,og cc 4゜7゜400゜2g 2g cc cc 140.0g 1.5cc 660.0cc (5 liquids) KBr 11
．． 8g NaCg
2. Add 5g Hio and 2
40cc (6 liquids) AgNOs 20.0gNH
4N0. (50%) Add 0.5cc HxO and make 200cc (1 liquid) 65%
The mixture was heated to ℃ and (2 liquids) were added. After that, (3 liquids)
and (4 liquids) were added simultaneously over a period of 50 minutes. 1 more
After 0 minutes, simultaneous addition was started for (liquid 5) for 12 minutes and (liquid 6) for 10 minutes. Five minutes after the addition was completed, the temperature was lowered and desalination was carried out. Add water and dispersed gelatin, adjust to pH 6.50, average particle size 0.46 μm, coefficient of variation (standard! Value obtained by dividing $ difference by average particle size; s/d) 0.0
9. Monodispersed cubic silver chlorobromide emulsion containing 90 mol% silver bromide (i
) was obtained.

Next, an unchemically sensitized emulsion (it) was obtained in the same manner as emulsion (i) except that the addition time of solution (5) was changed to 10 minutes.

Next, add 87.5 g of KBr (3) to the same <NaCj2
6.3g of liquid (5), 12.5g of KBr in liquid (5), same <N
An unchemically sensitized emulsion (iii) was obtained in the same manner as emulsion (i) except that aCj2 was changed to 1.0 g.

Next, (3) 55.0 g of KBr, 0.5 g of NaCn, 80 g of A g N Os (4) liquid, (5
) 45.0 g of KBr and 6.8 g of NaCA in the liquid
, (6) An unchemically sensitized emulsion (iv) was obtained in the same manner as in emulsion (i) except that the amount of A g N Oi in the solution was changed to 80 g.

The average grain size, coefficient of variation, and silver bromide content of each of these emulsions (if) to (iv) were the same as those of emulsion (i).

These unchemically sensitized emulsions (i) to (iv) were chemically sensitized with triethylthiourea while changing the type and amount of nucleic acid and pH conditions as shown in Table 1. The temperature was 50° C., and the time was selected at the point where the highest sensitivity was obtained under each condition. In addition, the nucleic acid (a) in the table was a ribonucleic acid (manufactured by Desumikokusaku Valve Co., Ltd., trade name: RNA-F), and the nucleic acid (b) was adenine. Note that sodium hydroxide was used to adjust the pH.

Note) Emulsion (i) Core/shell conversion emulsion Emulsion (iv) Core/shell conversion emulsion Emulsion (ii) Core/shell emulsion (no conversion applied) Emulsion (iii) ) Conversion emulsions (not core/shell emulsions) 13 types of emulsions A to M were coated on a cellulose triacetate base with a coated silver amount of 3.5 g/n and a coated gelatin amount of 5 g/n. did.

1 with white light at a color temperature of 5400 through a continuous wedge.
The film was exposed to light for 2 seconds, and the following development process was performed. The photographic density was measured with a densitometer, and the results shown in Table 2 were obtained.

Process Temperature Time Development 20°C 10 minutes fixation 20°C 3 minutes water washing 20°C 5 minutes Developer Ascorbic acid 10gp-methylaminophenol 2.4g Sodium carbonate
10g potassium bromide
Add tg water
II2 Fixer Sodium thiosulfate 300g Anhydrous sodium sulfite 15g Glacial acetic acid
Add 12g water
lε In Table 2, the sensitivity is expressed as the reciprocal of the exposure amount that gives an optical density 0.4 higher than the fog density, and is expressed as a relative value with the sensitivity of Emulsion A as 100. Further, the gradation was expressed as the difference in the logarithm of the exposure amount that gives an optical density that is 1.0 and 0.2 higher than the fog density, respectively.

Table (Note) The smaller the gradation value, the higher the contrast.

The following can be seen from the results in Table 2. As is clear from Emulsion A, chemical sensitization at a pH of 6.5 does not sufficiently increase sensitivity, resulting in low contrast and a lot of fog, and Emulsion F
As is clear, when the pH was 9.5, fog was suppressed, but the sensitivity was lowered and the contrast was also poor. In contrast, emulsions BE, G, and M of the present invention were , and chemical sensitization at a pH in the range of 7.0 to 9.0, it was possible to obtain performance with high contrast and less fogging. Further, it can be seen from the comparison with L that the present invention is extremely superior to emulsions with very low sensitivity and low contrast. Furthermore, as is clear from the cases of emulsions H1 and H1, if no nucleic acid is present during chemical sensitization, only poor sensitivity, contrast, and fog suppression can be obtained.

(Example 2) A multilayer color print sample having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

Layer structure The composition of each layer is shown below. The numbers represent coating weights (g/M); however, for silver halide emulsions, the coating weights are calculated in terms of silver.

Support polyethylene laminated paper [The polyethylene on the first layer side contains a white pigment (Tie-) and a bluish dye (ulmarine blue), 1st layer (blue-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-1) ) Monodisperse silver chlorobromide emulsion (EM-1 > 0.09 Monodisperse silver chlorobromide emulsion (EM-2) added with spectral sensitizer (Sen-1) 0.21 Antifoggant ( Cpd-1) 0.004 gelatin
1.28 Ij-0-coupler (E
xY) 0.68 antifoggant (Cpd-2
) 0.006 color image stabilizer (Cpd-3)
0.07 Solvent (Solv-1 and 5olv-2 volume ratio 1:1) 0.24 Second layer (
a color prevention M) Gelatin color mixing inhibitor (Cpd-4) Solvent (Solv-3 and 5olv-4 volume ratio 1:l) Third layer (edge-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-2, 3) Monodisperse silver chlorobromide emulsion antifoggant (Cpd-1) Antifoggant (Cpd-5) Gelatin magenta coupler (ExM) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd- 7) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Solvent (Solv-3 and 5olv-5 volume ratio l:2) Fourth ff (ultraviolet absorbing layer) Gelatin l, 34 0, 04 0,20 0.125 0,002 o,oot 1,47 0,32 0,10 0,08 0,03 0,004 0,65 1,43 Ultraviolet absorber (UV-1/2/3 molar ratio 1 :4:4) 0.47 Color mixing inhibitor (Cpd-4) 0.05 Solvent (So
l v-6) 0.24 Fifth layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion with added spectral sensitizer (Sen-4,5) 0.20 (EM-3
) 0.06 spectral sensitizer (S
0.14 antifoggant (Cpd-2) 0.008 antifoggant (Cpd-1o) 0.0001 antifoggant (Cpd-1o) Cp
d-11) 0.0001 gelatin
0.85 cyan coupler (ExC-1)
0.13 cyan coupler (ExC-2)
0.15 color image stabilizer (UV-1/3/4 molar ratio 1:3:3) 0.067 color image stabilizer (Cpd-3) 0.25 color image stabilizer (C
pd-7) 0.004 color image stabilizer (Cpd-
8) 0.007 solvent (Solv-1)
0.16 Sixth layer (ultraviolet absorption layer) Gelatin 0.38 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) o, 13 Solvent (
Solv-6) 0.06 Seventh layer (protective layer) Gelatin 1.25 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.05 Liquid paraffin 0.02 Silver halide emulsion used in the above sample Details are shown in Table 3.

Table 3 Coefficient of variation = standard deviation/average particle diameter (Sen-/3, rXlo-4%A//λg mol (Sen-, 2) λ, /X10-4 mol/person g mol (Sen-J) Hiroshi, 2 x 10-5 mol/Ag mol (ExY) (ExM) l:l mixture (mole ratio) (5en-Hiroshi) A, txio-5 mol/A g-el (S
en-yo) 2.3 x 10-3 mol/Ag mol (ExC-/) α (ExC-2) (Cpd-/) (Cpd-J) (Cpd-7) Molecular weight approximately to, oo.

(Cp d -II) (cpci-J') (Cp d -j) (Cpd-ta) Color image stabilizer (cpci-x) (JM shi1''i3 shii3 (Cp d-/0) (UV- ≠) (Cpd −// (Sol V −/ (UV−/) (Sol ■−2) 0=P (OCgHlg (iso) )3(Sol v−3) (UV−2) (Sol V−ψ ) (S o Lv-! ) C2Hs o=p-←()CH2CHC4H9)3(8o1v-1 C00CH2CHC4H9 2H5 As the gelatin hardening agent for each layer, l-oxy-3,5-
Dichloro50-S-) riazine sodium salt was used.

Furthermore, the following two types of dyes were used as irradiation-preventing dyes.

Based on the above layer structure, the third layer emulsion was prepared in Example-1.
Samples 201 to 21 were changed to emulsions A-M used in
3 was created.

A photosensitive needle (F manufactured by Fuji Photo Film Co., Ltd.) is attached to the above photosensitive material.
Gradation exposure for sensitometry was applied through a three-color separation filter using a WH type (light source color temperature: 3200K).

The exposure at this time was carried out at O, an exposure time of 1 second, and an exposure amount of 250 CMS. After exposure, the following processing steps were performed.

and processing steps temperature time color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Rinse for 1 minute and 30 seconds ■ Wash at 30-34℃ for 60 seconds Rinse at 030-34℃ for 60 seconds ■ Dry at 70-80℃ for 50 seconds (3-tank countercurrent force method for washing ■→■ 6) The composition of each treatment liquid is as follows.

L No. 2 Liyu Jusui 800
mFlood diethylenetriaminepentaacetic acid l, Og nitrilotriacetic acid 1.5g benzyl alcohol 15mA diethylene glycol l 0mg sodium sulfite
2.0g potassium bromide
0.5g Sumashun Potassium 30g
N-Ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline sulfate 5.0g Hydroxylamine sulfate 4.0g Optical brightener (WHT
TEX 4B (manufactured by Sumitomo Chemical ■) Add 1.0g water to 1000mρpH (25℃)
10.201 foot water 400m
Beta ammonium thiosulfate (70%) 150m β sodium sulfate 18g ethylenediaminetetraacetate iron (U+) Ammonium 55g ethylenediaminetetraacetate disodium 5g Add water to 1000mN pH (25℃)
6.70 Table 4 shows the measurement results for magenta images measured with a green filter. However, the sensitivity is expressed as the reciprocal of the exposure amount that gives an optical density 1°O higher than the fog density, and is relative to the sensitivity of sample 201 as 100. Shown as a value. The gradation was expressed as the difference in the logarithms of the exposure doses that give optical densities 1.0 and 0.2 higher than the fog density, respectively.

fjS4 table From this table, samples 202 to 205.207.21 of the present invention
3 was found to have high sensitivity, high contrast, and low fog.

(Example 3) Similar evaluations were performed on the sample of Example 2 except that the following development processing conditions were changed.

Melon Plate Crafts I l-degree Hitomi-ho color development
37℃ 3 minutes 30 seconds Bleach fixing 33℃
Washing for 1 minute and 30 seconds ■ Washing at 30-34°C for 60 seconds Washing at 30-34°C for 60 seconds ■ Drying at 70-80°C for 60 seconds (3-tank countercurrent system from washing ■ to ■). ) The composition of each treatment liquid is as follows.

Standing Erliyu Water 800m
β-Diethylenetriaminepentaacetic acid 1.0g Nitrilotriacetic acid 2.0g Benzyl alcohol Diethylene glycol Sodium sulfite Potassium bromide Potassium carbonate N-edyl N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline Sulfate Hydroxylamine Sulfate optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical ■) Add water to pH (25℃) Edamashi 1 water Ammonium thiosulfate (70%) Sodium sulfite iron ethylenediaminetetraacetate (■■) 5mQ 10mβ 2.0g 1.0g 0g 4゜g 3゜g l.

g 1000mI2 10.25 400mJl! 150+nJ2 8g Ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Add water
1000m100O (25℃)
6.70 The results were exactly the same as in Table 4, confirming the superiority of the sample according to the present invention.

(Example 4) When the sample of Example 2 was evaluated in the same manner with only the following development processing conditions changed, the same results as in Table 4 were obtained.

Melon Plate Craftsman's Eye Color Development
38℃ 1 minute 40 seconds Bleach fixing 35℃
Rinse for 60 seconds ■ 33-35℃ Rinse for 20 seconds 0 33
Rinse for 20 seconds at ~35°C Dry for 20 seconds at 33-35°C
70-80°C for 50 seconds The composition of each treatment solution is as follows.

1 liquid water diethylenetriamine pentaacetic acid nitrilotriacetic acid l-hydroxyethylidene-1,1-diphosphonic acid benzyl alcohol diethylene glycol sodium sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)- 3 Monomethyl-4-aminoaniline/sulfate Hydroxylamine/sulfate optical brightener (WHITEX 4B Add water to pH (25℃) 00ml11 1.0g 2.0g 2, Og 6mI2 LOmβ 2.0g o, 5g 0g 5,5g 2.0g 1000mβ 10.20 1 liquid water 400m
Beta ammonium thiosulfate (70%) 80m beta sodium sulfite 24g ethylenediaminetetraacetate iron (III) ammonium
Add 30g ethylenediaminetetraacetic acid disodium water and adjust to 1000mffpH (
25℃) 6.50cm long ion exchange water (calcium, magnesium each 3ppm
(Below) (Example-5) Emulsions A-M were used as the emulsions of the fifth layer (red-sensitive emulsion layer) in the sensitive materials of Examples to 12 and compared, and it was found that the cyan images were also found in Example-5. Results similar to 2 were obtained.

(Example-6) In the photosensitive material of Example-2, emulsions A to M were used as the emulsions of the -th layer (blue-sensitive emulsion layer) and were compared. obtained similar results.

(Effects of the Invention) As is clear from the results of the above examples, the present invention makes it possible to provide an excellent silver halide photographic material with high sensitivity, high contrast, and low fog photographic performance. becomes. This product also has excellent pressure resistance.

Claims (1)

[Claims] Silver halide grains that are made of silver chlorobromide that does not substantially contain silver iodide and have multiple partial structures with different halogen compositions are subjected to halogen conversion on the surface, and after desalting treatment, nucleic acids or their decomposition products are produced. pH7.0-9 in the presence of substances
．． 1. A silver halide photographic light-sensitive material, characterized in that at least one emulsion layer on a support contains a silver chlorobromide emulsion obtained by chemical sensitization in the range of 0.