JPH0711681B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material excellent in pressure resistance and suitable for rapid processing.

BACKGROUND OF THE INVENTION In a method of forming a dye image, which usually uses a silver halide color photographic light-sensitive material, p-oxidized after imagewise exposure is applied.
A phenylenediamine color developing agent is reacted with a dye image-forming coupler to form a dye image. In this method, a color reproduction method is usually applied by a subtractive color method, and cyan, magenta, and yellow dye images corresponding to red, green, and blue are formed on respective photosensitive layers. In recent years, in forming such a dye image, in order to shorten the development processing time, high-activity development processing such as high-pH, high-temperature, high-concentration color developing agent and the processing step are generally omitted. It is like this. In particular, in order to shorten the development processing time by the high activity development processing, it is very important to improve the development speed in color development.

Therefore, in recent years, various measures have been taken to speed up color development. As one of the methods, it is known to use a development accelerator when an exposed silver halide color photographic light-sensitive material is developed using an aromatic primary amine type color developing agent. Of these development accelerators, the compounds with a relatively high degree of activity often suffer from fog formation. However, among these compounds, certain black-and-white developing agents that exhibit superadditivity in color development can obtain a development accelerating effect with relatively low fog formation as compared with other development accelerators.
Examples of such black and white developing agents include British Patent 811,185.
1-phenyl-3-pyrazolidone described in U.S. Pat.
N-methyl-p-aminophenol described in No. 417,514,
N, N, N ', N'-tetramethyl-described in JP-A-50-15554
Examples include p-phenylenediamine. For the mechanism of super-additive development in this color development, see GF Van Veelen
By Journal of the Photographic
Science, No. 20, p. 94 (1972).
As a method for obtaining a color development accelerating effect by using such a black and white developing agent as an auxiliary developer, there are a case where it is contained in advance in a silver halide color photographic light-sensitive material and a case where it is contained in a color developing solution. There is.

Of these, 1-aryl-3-pyrazolidones are particularly preferably used when the above-mentioned black-and-white developing agent is included in the silver halide photographic light-sensitive material in order to accelerate color development. For example, JP-A-56-89739 discloses a 1-aryl-containing silver halide color photographic light-sensitive material having a silver halide emulsion layer in which the grain size ratio of silver halide grains is different by 50% or more on a support. The addition of 3-pyrazolidone is disclosed. However, the silver halide color photographic light-sensitive material containing 1-aryl-3-pyrazolidone disclosed in this publication is used for intensification processing in the presence of an intensifying agent such as a cobalt complex salt. When it is processed for ordinary color development processing, its development acceleration effect is extremely insufficient. Especially, when a silver halide emulsion having silver halide grains having a large average grain size is used, the ordinary color development processing is performed. It was found that the effect of promoting color development can hardly be obtained in the case of carrying out.

Further, JP-A-56-64339 discloses a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and further JP-A-57-144547.
No. 58, No. 58-5032, No. 58-50533, No. 58-50534,
JP-A-58-50535 and JP-A-58-50536 disclose that 1-aryl-3-pyrazolidones are added to a silver halide color photographic light-sensitive material and processed within an extremely short developing time. Has been done.

However, even though each of the techniques described in these publications can be satisfied in that they merely obtain a development-accelerating effect, they are not always satisfactory when comprehensively considering photographic performance such as sensitivity, gradation, and maximum density. It's hard to say that there was.

On the other hand, regarding silver halide emulsions having silver halide grains used in silver halide photographic light-sensitive materials, it has been found that the shape, size, and composition of silver halide grains have a great influence on the development speed. , Various studies have been made. Among them, it has been found that the high temperature silver halide grains show remarkably high developability under certain specific conditions, and the use of the high chloride silver halide grains is more preferable than the use of the above-mentioned development accelerator. It is advantageous with few drawbacks. Therefore, various kinds of high temperature silver halide emulsions have been conventionally studied in order to shorten the development processing time.

However, the high chloride silver halide emulsion has significantly faster developability than the silver bromide emulsion or the silver iodobromide emulsion, but on the other hand, it has the disadvantages of low sensitivity and easy fog. It was a big problem in practical application.

Numerous methods have been proposed for the purpose of remedying these drawbacks. For example, JP 55-135832, British Patent 1,495,
No. 753, etc., a method of combining metal ions with high chloride silver halide grains, JP-A-58-95736, JP-A-60-222844,
No. 60-222845, etc., a method of using a laminated high chloride silver halide emulsion having a layer mainly made of silver bromide, and Japanese Patent Laid-Open Nos. 58-95340 and 58-107531 disclose high chlorides. A method of combining a silver halide emulsion and a sensitizing dye is disclosed.

However, these methods are not always satisfactory because the effects are insufficient and other photographic performances are adversely affected.

In particular, the high chloride silver halide emulsions are other silver bromide emulsions,
It has the drawback of being inferior in pressure resistance as compared with the silver iodobromide emulsion.

The pressure characteristics of silver halide grains will be described below.

Generally, various pressures are applied to the light-sensitive material. When manufacturing the photosensitive material, a great pressure is applied, for example, in the step of cutting the photosensitive material.

In addition, when the photosensitive material is used, the sheet-shaped photosensitive material is often bent because humans handle it by hand, and pressure is applied to the bent portion.

On the other hand, it has become more common in recent years to subject a photosensitive material to automatic exposure by a printer and automatic development processing using an automatic processor. As a result, the photosensitive material is increasingly exposed to mechanical pressure in these devices. When various pressures are applied to the light-sensitive material in this manner, pressure is also applied to the silver halide grains in the light-sensitive material through gelatin which is a binder of the silver halide grains. When pressure is applied to silver halide grains, photographic characteristics are changed, and phenomena such as pressure desensitization and pressure fog occur. This phenomenon is well known in the art as the photographic pressure effect, for example, TH James: The Theory of the Photographic Proces.
s), 4th edition, Macmillan Publishers, New York, 24th
Page, D. Dautrich, F. Granzer and E. Moisa
r): Journal of Photographic Science (J.Phot.Sci.), 21,221 (1973), etc.

Further, it is well known in the art that the larger and more sensitive silver halide grains are more sensitive to pressure and more likely to cause pressure desensitization and pressure fog.

Furthermore, when the light-sensitive material is applied with pressure in a dry state,
In some cases, pressure is applied in a wet state during the development process. Therefore, the effect cannot be said to be sufficient unless the pressure resistance is improved in both states.

Therefore, it has been attempted to provide a light-sensitive material that has little influence on pressure.

As a means for improving the pressure characteristics, a method of incorporating a plasticizer such as a polymer and a method of reducing the silver halide / gelatin ratio are known.

For example, British Patent No. 738,618 describes a heterocyclic compound as 738,6
No. 37 is an alkyl phthalate, No. 738,639 is an alkyl ester, U.S. Pat.No. 2,960,404 is a polyhydric alcohol, U.S. Pat. Japanese Patent Publication No. 53-28086 discloses a method of using an acid salt and an alkyl acrylate and an organic acid.

However, these techniques have the drawbacks that the pressure resistance effect is insufficient in both the dry state and the wet state, and further the binder properties such as stickiness and drying property on the surface of the photosensitive material are significantly deteriorated.

Further, as a means for improving the pressure characteristics of silver halide grains, JP-B-57-23248 discloses a method of adding a mercapto compound and a water-soluble iridium compound during the formation of silver halide grains, and U.S. Pat. The method of using the modified emulsion thus prepared is disclosed.

However, these techniques cannot obtain a satisfactory pressure resistance effect in both the dry state and the wet state.

Further, in these techniques, the pressure resistance effect decreases as the sensitivity increases or the grain size of silver halide grains increases.

Therefore, in order to maintain the superiority of the high chloride silver halide grains and to improve the pressure characteristics in both the dry state and the wet state, none of the conventional techniques is sufficiently effective, and further improvement is desired. It was rare.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material excellent in pressure resistance in both a dry state and a wet state and suitable for rapid processing. Still other objects will become apparent from the description below.

[Constitution of the Invention] The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is silver halide 1. Silver halide containing high silver chloride grains having a silver chloride content of 80 to 99 mol%, in which a metal ion of 10 ^-8 to 10 ^-5 mol per mol and a phase containing high silver bromide are localized outside the grain. It could be achieved by using a photographic light-sensitive material.

[Specific Structure of the Invention] In the silver halide photographic light-sensitive material of the present invention, the silver halide grains contained in at least one of the silver halide emulsion layers have a silver chloride content of 80 mol% to 99 mol%. High silver chloride phase, which is a silver particle and constitutes the majority of the particle,
And a high silver bromide phase localized and present on the surface of the grain.

The term "localization" used herein means that, when the silver halide grains are analyzed by an X-ray diffraction method, a peak attributed to the high silver bromide phase is attributed to a high silver chloride phase other than the high silver bromide phase. It shows a diffraction pattern that can be clearly distinguished from the peaks.

The silver bromide composition of the high silver bromide phase is preferably 70 mol% or more. More preferably, it is 90 mol% or more. Further, the ratio of the high silver bromide phase in one halogenated grain is 0.5
To 20 mol%, more preferably 1 to 10 mol%.

The silver halide grains having the high silver bromide phase as a localized phase may be those in which the high silver bromide phase and the high silver chloride phase have a layered structure, or silver halide grains composed of the high silver chloride phase are formed. After that, a high silver bromide phase may be epitaxially grown on the crystal surface of the grain so as not to completely cover the crystal surface.

The high silver bromide phase may form two or more localized phases in one silver halide grain. The composition may change discontinuously or continuously at the boundary between the high silver bromide phase and the high silver chloride phase.

The silver halide grains having a highly bromide localized phase of the present invention (hereinafter referred to as “silver halide grains of the present invention”) may be used alone or in combination with other silver halide grains. Good.

When the silver halide grains of the present invention are used in a mixture with the silver halide grains of the present invention, the projected area occupied by all the silver halide grains of the silver halide emulsion layer containing the silver halide grains of the present invention, The projected area ratio occupied by the silver halide grains of the present invention is preferably 50% or more, more preferably 75% or more.

Such silver halide grains include, for example, JP-A Nos. 59-162540, 59-48755, 60-222844, and 60.
It can be formed according to the method described in, for example, JP-A-222845 and JP-A-60-136735.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. In addition, US patent
4,183,756, 4,225,666, JP-A-55-26589,
Statements such as Japanese Examined Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photgr.Sc
i), 21 , 39 (1973), etc.
It is also possible to make particles having a shape such as an octahedron, a tetrahedron, a dodecahedron, and use the particles. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.
It is in the range of 25 to 1.2 μm. The particle size can be measured by various methods generally used in the technical field. A typical method is Loveland's "Particle Size Analysis" ASTM Symposium on Light Microscopy, 1955, pp. 94-122 or "Theory of Photographic Processes", Co-authored by Mies and James, Third Edition, Macmillan Company. It is described in Chapter 2 of the publication (1966).

This particle size can be measured using the projected area of the particle or a direct approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Monodispersed silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Here, ri represents the particle size of each particle, and ni represents the number. The term "particle size" used herein refers to the diameter of spherical silver halide grains, and the diameter of a cubic image or a grain having a shape other than spherical when the projected image is converted into a circular image of the same area. .

Metal ions are further added to the silver halide grains according to the present invention in an amount of 10 ⁻⁸ to 10 ⁻⁵ mol per mol of silver halide.

The metal ion used in the present invention is not particularly limited, but preferably cadmium, lead, copper, zinc, rhodium,
Palladium, iridium, platinum, thallium, iron, etc. are used. These metal ions are preferably used in the form of a metal salt or a metal complex salt.

The addition amount is 10 as described above per 1 mol of silver halide.
^-8 to 10 ^-5 mol, and in this range, the optimum amount is appropriately selected in combination with the grain size of the silver halide grains, crystal habit, and further in combination with other additives such as a sensitizing dye. In general
If it is less than 10 ^-8 mol, the effect of the present invention cannot be sufficiently exerted,
^{If the} amount exceeds ^-5 mol, other photographic properties such as desensitization may be adversely affected.

The metal ion used in the present invention may be added at any stage of nucleation, grain growth and physical ripening of the silver halide grain of the present invention, or may be dividedly added. These metal ions are used in the form of metal salts or metal complex salts, and these compounds are dissolved in water or a suitable solvent and added.

Among the metal ions used in the present invention, iridium is particularly preferable, and specific compounds include iridium trichloride, iridium tetrachloride, hexachloroiridium (II
Examples thereof include potassium I) acid, potassium hexachloroiridium (IV) acid, and ammonium hexachloroiridium (III).

In the present invention, 10 ^-8 per mol of the silver halide.
~ 10 ^-5 mol of metal ions and a silver halide emulsion containing high silver chloride grains having a silver chloride content of 80 to 99 mol% having a high silver bromide-containing phase provide not only pressure resistance in a dry state but also during development processing. It was surprising that the pressure resistance in wet conditions such as is also improved.

The silver halide grains according to the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halogen salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method is preferable. Furthermore, as one type of simultaneous mixing method, Japanese Patent Laid-Open No.
It is also possible to use the pAg-controlled doubly jet method described in US Pat.

If necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grain according to the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

However, in order to sufficiently bring out the effect of the present invention, when chemical sensitization is carried out after silver halide grain formation, that is, before chemical sensitization, and when chemical sensitization is carried out during silver halide grain formation, After the silver particles are finally formed,
It is preferred to avoid applying silver halide grains of the type that primarily form a latent image therein. In order to judge whether or not the silver halide grains are of the internal latent image type, it may be evaluated according to the method described in JP-B-52-34213.

That is, the emulsion to be evaluated is coated on a polyethylene-coated support at a silver coverage of about 300-400 mg / ft ² . This sample was divided into two, and each was subjected to a light-intensity scale to obtain 1 × 10 ^-2
Exposure is carried out using a 500 W tungsten lamp for a fixed time of 1 second. One of the samples is the following developer Y
(“Internal type” developer) 18.3 ° C., 5 minutes development, the other one is the following developer X (“surface type” developer) 20
Develop at 6 ° C for 6 minutes.

In the present invention, it is preferable to use silver halide grains in which the maximum density after internal development / the maximum density after surface development is 5 or less, and more preferably 2 or less.

Developer X N-methyl-p-aminophenol sulphate 2.5g Ascorbic acid 10.0g Potassium metaborate 35.0g Potassium bromide 1.0g Add water 1 (pH = 9.6) Developer Y N-methyl-p-aminophenol sulphate 2.0g Sodium sulfite (dry) 90.0g Hydroquinone 8.0g Sodium carbonate / 1H ₂ O 52.5g Potassium bromide 5.0g Potassium iodide 0.5g Add water 1 (pH = 10.6) The silver halide grains according to the present invention And a silver halide emulsion containing the above metal ions in an amount of 10 ^-8 to 10 ^-5 mol per mol of silver halide (hereinafter referred to as a silver halide emulsion of the present invention) is unnecessary after the growth of silver halide grains is completed. Soluble salts may be removed or may remain contained. The salts can be removed by the method described in Research Disclosure No. 17643.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method using a selenium compound, the reduction sensitization method using a reducing substance, the noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be spectrally sensitized in a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is preferably spectrally sensitized with a sensitizing dye represented by the following general formula [A].

General formula [A] In the general formula [A], Z ₁₁ and Z ₁₂ are a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus and a pyridine nucleus, respectively. Or, it represents a group of atoms necessary for forming a quinoline nucleus, and these heterocycles include those having a substituent. Examples of the substituent of the heterocycle formed by Z ₁₁ and Z ₁₂ include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group or an alkoxycarbonyl group, and among these substituents, preferable substituents are , A halogen atom, a cyano group, an aryl group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and particularly preferable substituents are a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

R_{twenty one}And R_{twenty two}Are alkyl and alkenyl groups, respectively.
Or an aryl group, preferably an alkyl group.
And more preferably a carboxyl group or a sulfo group
Substituted alkyl group, most preferred carbon atom
It is a sulfoalkyl group having a child number of 1 to 4. Also R_{twenty three}Is hydrogen
It is selected from an atom, a methyl group and an ethyl group. X Is Yin Io
And 1 represents 0 or 1.

Among the sensitizing dyes represented by the general formula [A], particularly useful dyes are the sensitizing dyes represented by the following general formula [A '].

General formula [A '] Here, Y ₁ and Y ₂ each represent an atom group necessary for completing an optionally substituted benzene ring or naphthalene ring. The benzene ring and naphthalene ring formed by Y ₁ and Y ₂ also include those having a substituent, and the substituent is preferably a halogen atom, a hydroxyl group, a cyano group, an aryl group,
It is an alkyl group, an alkoxy group or an alkoxycarbonyl group. More preferred substituents are halogen atoms, cyano groups, aryl groups, alkyl groups or alkoxy groups having 1 to 6 carbon atoms, and particularly preferred substituents are halogen atoms, cyano groups, methyl groups, ethyl groups, methoxy groups or ethoxy groups. Is.

R_{twenty one}, R_{twenty two}, R_{twenty three}, X And l are represented by the general formula [A]
It is the same as

Specific examples of the sensitizing dye represented by the general formula [A] used in the present invention are shown below.

General formula [A] When the silver halide emulsion according to the present invention is used as a green-sensitive emulsion, it is preferably spectrally sensitized with a sensitizing dye represented by the following general formula [B].

General formula [B] In the formula, Z ₁₁ and Z ₁₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring condensed with an oxazole. The heterocyclic nucleus formed may be substituted with various substituents, and these preferable substituents are a halogen atom, an aryl group, an alkyl group or an alkoxy group. More preferable substituents are a halogen atom, a phenyl group and a methoxy group, and the most preferable substituent is a phenyl group.

According to a preferred embodiment of the present invention, Z ₁₁ and Z ₁₂ both represent a benzene ring fused to an oxazole ring, and at least one of these benzene rings has a 5-position substituted with a phenyl group, or The 5-position of one benzene ring is substituted with a phenyl group and the 5-position of the other benzene ring is substituted with a halogen atom.

R ₂₁ and R ₂₂ each represent an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group. More preferably, R ₂₁ and R ₂₂ are each an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. Most preferably, it is a sulfoethyl group.

R ₂₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
It preferably represents a hydrogen atom or an ethyl group.

X₁ Represents an anion, for example, chlorine, bromine, iodine
Halogen ions,CH₃SO_Four, C₂H_FiveSO_FourAnd the like anions. n is 1
Or represents 0. However, when the compound forms an inner salt
In this case, n represents 0.

Hereinafter, specific examples of the sensitizing dye represented by the general formula [B] which is preferably used in the invention will be shown.

When the silver halide emulsion according to the present invention is used as a red-sensitive emulsion, it may be spectrally sensitized with a sensitizing dye represented by the following general formula [C] or a sensitizing dye represented by the following general formula [D]. preferable.

General formula [C]General formula [D]In the formula, R represents a hydrogen atom or an alkyl group, and R₁Through
R_FourRepresents an alkyl group and an aryl group, respectively, and Z₁,
Z₂, Z_FourAnd Z_FiveIs a thiazole ring or selenazo, respectively
Form a benzene or naphthalene ring fused to a ring
Represents the atomic group necessary for₃Is necessary to form a 6-membered ring
Represents a necessary hydrocarbon atom group, l represents 1 or 2,
Z represents a sulfur atom or a selenium atom, and X Is an anion
Represents

In the above general formula, the alkyl group represented by R includes a methyl group, an ethyl group and a propyl group, and R is preferably a hydrogen atom, a methyl group or an ethyl group. Particularly preferred are hydrogen atom and ethyl group.

Further, R ₁ , R ₂ , R ₃ and R ₄ are each a linear or branched alkyl group, and this alkyl group may have a substituent.
(For example, methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl,
Carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroxy-γ-sulfopropyl, sulfatepropyl, allyl, benzyl, etc.) or an aryl group, even if this aryl group has a substituent Good. (For example, phenyl, carboxyphenyl, sulfophenyl, etc.) represents a group selected from, and the heterocyclic nucleus formed by Z ₁ , Z ₂ , Z ₄ and Z ₅ may have a substituent,
The substituent is preferably a halogen atom, an aryl group, an alkyl group or an alkoxy group, more preferably a halogen atom (eg chlorine atom), a phenyl group or a methoxy group.

X is an anion (eg Cl, Br, I, CH ₃ SO ₄ , C ₂ H ₅ SO _4, etc., and 1 represents 1 or 2.

However, 1 represents 1 when the compound forms an inner salt.

Hereinafter, typical specific examples of the sensitizing dyes represented by the general formulas [C] and [D] which are preferably used in the invention will be shown.

The general formula [A], [B], [C] , or the addition amount of the sensitizing dye represented by [D] is not particularly limited, generally 1 mol of silver halide per 1 × 10 ^-7 ~1 × 10 ^- It is preferably used in the range of ³ mol, more preferably 5 × 10 ^{−6 to} 5 ×
It is 10 ^-4 mol.

As a method of adding a sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes are dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or a mixture of such solvents), and in some cases diluted with water, or In some cases they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibration for this dissolution. Further, the sensitizing dye used in the present invention, as described in US Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid,
A method of adding this dispersion, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion, as described in JP-B-46-24185 and the like, can also be used. Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution dispersion method. Other addition methods are described in U.S. Pat.
The methods described in 3,342,605, 2,996,287, 3,425,835 and the like can also be used.

The sensitizing dye contained in the silver halide emulsion of the present invention may be dissolved in the same or different solvent, and these solutions may be mixed or added separately prior to addition to the silver halide emulsion. . When they are added separately, their order, time, and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion production process, but is preferably added during or after chemical ripening, and more preferably during chemical ripening.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
A silver halide emulsion during and after the chemical ripening and / or after the chemical ripening for the purpose of preventing fog during storage or photographic processing and / or keeping the photographic performance stable. By the time of coating, compounds known as antifoggants or stabilizers in the photographic industry can be added.

Further, in the silver halide emulsion of the present invention, a mercapto heterocyclic compound represented by the following general formula [I] can be preferably used in order to efficiently achieve the effects of the present invention.

General formula [I] Z _o —SH (In the formula, Z _o represents a heterocyclic residue.) The heterocyclic residue represented by Z _o in the general formula [I] may have a substituent, Examples of this substituent include an alkyl group, an aryl group, an alkenyl group, a sulfamoyl group, a carbamoyl group, and an acyl group.

In the mercapto heterocyclic compound represented by the general formula [I] used in the present invention, preferably used are
It is a mercapto heterocyclic compound represented by the following general formula [Ia].

General formula [Ia] In the formula, Z _o ′ is an imidazoline ring, an imidazole ring, an imidazolone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, a thiazole ring, a thiazolone ring, a selenazoline ring, a selenazole ring, and a selenazolone. Ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, pyrazine ring,
Pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring and polyazaindene ring (eg, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc.), etc. Represents the group of atoms necessary to form a ring.

Of the general formula [Ia] The heterocyclic residue represented by may have the same substituents as those represented by Z _o in the above general formula [I].

The mercapto heterocyclic compound represented by the general formula [Ia] is more preferably a mercaptotriazole compound having a triazole ring.

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the invention is not limited thereto.

Exemplified mercapto heterocyclic compound The mercapto heterocyclic compound represented by the general formula [I] preferably used in the present invention is, for example, JP-B-48-42974,
57-51666, JP-A-48-102621, French Patent No. 7
01,053, 701,301, 1,563,019, U.S. Pat.
457,078 and The Journai of Photograhic Sci
ence) 19.p83-87 etc.

The addition amount of the mercapto heterocyclic compound preferably used in the present invention may vary widely depending on the conditions of the silver halide emulsion, for example, the content of silver chloride, the grain size, the crystal form, etc., but 1 × 10 ⁻ per mol of silver halide. ⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol show good results. Further, as an addition method, a usual method for adding photographic additives,
For example, it is dissolved in water, an acid or alkali aqueous solution having an appropriate pH value, or an organic solvent such as methanol or ethanol and added to the silver halide emulsion.

The mercapto heterocyclic compound preferably used in the present invention may be used singly or in combination of two or more kinds, and it is also possible to additionally add other compounds known as antifoggants or stabilizers in the photographic industry. .

Regarding the addition position of the heterocyclic compound preferably used in the present invention, any effect can be obtained in the silver halide emulsion layer of the present invention and / or the other photographic constituent layers, and particularly in the silver halide emulsion layer of the present invention. It is preferably used.

The timing of addition to the silver halide emulsion layer is not particularly limited, but it is preferably from after the completion of chemical sensitization to immediately before the coating of the silver halide emulsion. But it doesn't matter.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative and positive film, a color photographic paper, and the like. In particular, the method of the present invention is applied to a color photographic paper directly provided for viewing. The effect of is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, it is usually used as a photographic coupler in order to reproduce color by the decoloring method.
A silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-photosensitive layer are laminated on a support in an appropriate number and order of layers. The order of layers may be appropriately changed depending on the priority performance and purpose of use.

When the silver halide photographic light-sensitive material of the present invention is a multicolor color light-sensitive material, the layer structure of the silver halide emulsion layer, that is, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive light-sensitive material The layer order of the photosensitive emulsion layer is arbitrary, and the non-photosensitive layer other than the protective layer of the present invention (for example, an intermediate layer, a filter layer, an irradiation prevention layer, etc.) is arbitrary,
As a preferred specific layer structure, a yellow dye image forming layer, a first intermediate layer, a magenta dye image forming layer, a second intermediate layer containing an ultraviolet absorber, and a cyan dye image are formed on a support in order from the upper side of the support. It is arranged with a forming layer, an intermediate layer containing an ultraviolet absorber, and a protective layer.

As the yellow dye forming coupler used in the present invention, known acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include British Patent No. 1,077,874, JP-B-45-40757, and JP-A-47-1031.
No. 47, No. 47-26133, No. 48-94432, No. 50-87650,
51-3631, 52-115219, 54-99433, 54
-133329, 56-30127, U.S. Pat.No. 2,875,057,
3,253,924, 3,265,506, 3,408,194, 3,5
51,155, 3,551,156, 3,664,841, 3,725,07
No. 2, No. 3,730,722, No. 3,891,445, No. 3,900,483,
3,929,484, 3,933,500, 3,973,968, 3,9
90,896, 4,012,259, 4,022,620, 4,029,50
No. 8, No. 4,057,432, No. 4,106,942, No. 4,133,958,
4,269,936, 4,286,053, 4,304,845, 4,3
14,023, 4,336,327, 4,356,258, 4,386,15
5, No. 4,401,752, etc.

The yellow dye-forming coupler used in the present invention is preferably represented by the following general formula [Y].

General formula [Y] In the formula, R ₁ represents a halogen atom or an alkoxy group. R ₂
Represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. R ₃ is an optionally substituted acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group or Represents an aryloxy group. Z ₁ represents a group capable of splitting off upon coupling with an oxidized product of a color developing agent.

In the present invention, as the magenta dye-forming coupler,
The couplers represented by the following general formulas [M-1] and [M-2] can be preferably used.

General formula [M-1] [In the formula, Ar represents an aryl group, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a substituent. Y represents a hydrogen atom or a substituent capable of splitting off upon reaction with oxidative rest of the color developing agent, W represents -NH-, -NHCO- (N atom is bonded to carbon atom of pyrazolone nucleus) or -NHCONH-, m is an integer of 1 or 2. ) The above general formula [M-2] general formula [M-2] In the magenta coupler represented by, Za represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Za may have a substituent.

Y represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent.

R ₁ represents a hydrogen atom or a substituent.

The substituent represented by R ₁ , for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group , Carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an alkylthio group, an arylthio group and a heterocyclic thio group.

These are, for example, U.S. Patent Nos. 2,600,788 and 3,061,4.
No. 32, No. 3,062,653, No. 3,127,269, No. 3,311,
No. 476, No. 3,152,896, No. 3,419,391, No. 3,51
No. 9,429, No. 3,555,318, No. 3,684,514, No. 3,8
88,680, 3,907,517, 3,928,044, 3,
930,861, No. 3,930,866, No. 3,933,500, etc., JP-A-49-29639, 49-111631, 49-129
538, 50-13041, 52-58922, 55-62454
No. 55, No. 55-118034, No. 56-38043, No. 57-35858,
60-23855 publications, British patent 1,247,493, Belgian patent 769,116, the same 792,525, West German patent 2,156,
No. 111, JP-B-46-60479, JP-A-59-125,
732, 59-228,252, 59-162,548, 59-17
1,956, 60-33,552, 60-43,659 publications,
It is described in each specification of West German Patent 1,070,030 and US Patent 3,725,067.

Cyan dye image forming couplers include phenolic compounds,
A naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming coupler is typical, and US Pat. No. 2,306,410,
No. 2,356,475, No. 2,362,598, No. 2,367,531
No. 2,369,929, 2,423,730, 2,474,29
No. 3, No. 2,476,008, No. 2,498,466, No. 2,545,6
No. 87, No. 2,728,660, No. 2,772,162, No. 2,895,
No. 826, No. 2,976,146, No. 3,002,836, No. 3,41
No. 9,390, No. 3,446,622, No. 3,476,563, No. 3,7
Nos. 37,316, 3,758,308, 3,839,044, British Patents 478,991, 945,542, 1,084,480, 1,377,233, 1,388,024 and 1,543,040, and special specifications. Kaisho 47-37425, ibid. 50-10135
No. 50, No. 50-25228, No. 50-112038, No. 50-117422
No. 50, No. 130-441, No. 51-6551, No. 51-37647,
51-52828, 51-108841, 53-109630, 5
4-48237, 54-66129, 54-131931, 55-3
2071, 59-146050, 59-31953 and 60-117
It is described in various publications such as No. 249.

As the cyan dye image-forming coupler, the following general formula [C
-1] and [C-2] can be preferably used.

General formula [C-1] In the formula, R ₁ represents an aryl group, a cycloalkyl group or a heterocyclic group. R ₂ represents an alkyl group or a phenyl group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Z ₁ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

General formula [C-2] In the formula, R ₄ represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R ₅ represents an alkyl group (eg, methyl group, ethyl group, etc.). R ₆ is a hydrogen atom, a halogen atom (eg fluorine, chlorine, bromine etc.) or an alkyl group (eg methyl group, ethyl group etc.)
Represents Z ₂ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent.

For the hydrophobic compound such as a dye-forming coupler which does not need to be adsorbed on the surface of the silver halide crystal, various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used. Can be appropriately selected according to the chemical structure of the hydrophobic compound such as The oil-in-water emulsion dispersion method can be applied by a conventionally known method of dispersing a hydrophobic additive such as a coupler, usually, a high boiling point organic solvent having a boiling point of about 150 ° C. or higher, a low boiling point if necessary, and / or Dissolve it in combination with a water-soluble organic solvent, and use a surfactant in a hydrophilic binder such as an aqueous gelatin solution with a dispersing means such as a stirrer, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion liquid or dispersion.

As a high-boiling organic solvent, a phenol derivative that does not react with an oxidized product of a developing agent, a phthalic acid alkyl ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester, a trimesic acid ester or the like having a boiling point of 150 ° C. or higher. An organic solvent is used.

The high-boiling organic solvent that can be used in the present invention,
U.S. Pat.Nos. 2,322,027, 2,533,514, 2,835,579
No. 3,287,134, 2,353,262, 2,852,383,
3,554,755, 3,676,137, 3,676,142, 3,7
00,454, 3,748,141, 3,779,765, 3,837,86
3, British Patents 958,441, 1,222,753, OLS 2,538,88
9, JP-A-47-1031, JP-A-49-90523, JP-A-50-23823
No. 51-26037, No. 51-27921, No. 51-27922,
51-26035, 51-26036, 50-62632, 53
-1520, 53-1521, 53-15127, 54-11992
No. 1, 54-119922, 55-25057, 55-36869
No. 56-19049, No. 56-81836, No. 48-29060
No. etc.

Low-boiling or water-soluble organic solvents that can be used with or instead of high-boiling solvents are described in U.S. Patent Nos. 2,801,171 and 2,942.
Examples include those described in No. 9,360. The low boiling point substantially water-insoluble organic solvent includes ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and the water-soluble organic solvent includes acetone, Methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate,
Methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide,
Hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol and the like can be mentioned as examples.

As the latex dispersion method, for example, U.S. Pat.
No. 3, No. 4,214,047, No. 4,203,716, No. 4,247,627,
JP-A-49-74538, 51-59942, 51-59943,
The method described in JP-A-54-32552 is preferable.

Examples of the surfactant used as a dispersion aid include alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyoxyethylene. Anionic surfactants such as alkylphenyl ethers, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkyl sulfonic acids,
It is preferable to use amphoteric surfactants such as and alkyl betaines, and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants are described in "Surfactant Handbook" (Sangyo Tosho, 1966).
Year)) and "Emulsifier. Emulsifier Research. Technical Data Collection" (Kagakugenron, 1978).

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in an amount capable of hardening the photosensitive material to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

In the silver halide photographic light-sensitive material of the present invention, the compound represented by the following general formula [II] or the following general formula [III]
The compound represented by is preferably used as a hardener.

General formula [II] [Wherein R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an —OM group (M is a monovalent metal atom), and a —NR′R ″ group (R ′ and R ″ are each hydrogen. Atom, an alkyl group, or an aryl group) or a --NHCOR group (R represents a hydrogen atom, an alkyl group, or an aryl group), and R ₂ represents a group having the same meaning as R ₁ described above except a chlorine atom. . ] General formula [III] [In the formula, R ₃ and R ₄ each represent a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or an —OM group (M is a monovalent metal atom). Q and Q'are -O-,
Represents a linking group representing -S- or -NH-, and L represents an alkylene group or an arylene group. l and m each represent 0 or 1. The compound represented by the general formula [II] or [III] used in the present invention will be described in detail.

In the general formulas [II] and [III], examples of the alkyl group component of the alkyl group represented by R ₁ and the alkoxy group and the alkylthio group include an alkyl group having 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group and an ethylthio group.

Examples of M representing a monovalent metal atom of the —OM group represented by R ₁ include, for example, sodium, potassium, ammonium and the like, and as an alkyl group represented by R ′ and R ″ of the —NR′R ″ group. Is an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group, and the aryl group is a phenyl group.

Further, the alkyl group and the aryl group represented by R of the --NHCOR group represented by R ₁ are the same as the above R ′ and R ″.
Is a group having the same meaning as the alkyl group and aryl group represented by.

R ₂ is a group having the same meaning as R ₁ described above except for a chlorine atom as described above.

Next, the groups represented by R ₃ and R ₄ are the same as the groups represented by R ₁ above. Examples of the alkylene group represented by L include alkylene groups having 1 to 3 carbon atoms, such as methylene group and ethylene group. Examples of the arylene group include a phenylene group.

Next, typical examples of the compounds of the present invention represented by the above general formulas [II] and [III] will be described.

The compound represented by the general formula [II] or [III] used in the present invention may be used alone or in combination of two or more kinds, and the addition amount thereof is 0.5 to 100 m per 1 g of coated gelatin.
g, preferably 2 to 50 mg.

The above compound is dissolved in water or alcohols such as methanol and ethanol and added.

The addition method may be either a batch method or an in-line method.

Regarding the compound represented by the general formula [II], U.S. Pat. No. 3,645,743, JP-B-47-6151, and JP-A-47-33380,
51-9607, JP-A-48-18220, 51-78788,
52-60612, 52-128130, 52-130326, 56
No. 1043, etc., and it can be used in light of the above criteria.

A plasticizer may be added for the purpose of increasing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly-soluble synthetic polymer for the purpose of improving dimensional stability. Can be done.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (same color-sensitive layers and / or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent moves to cause color turbidity or sharpness. An anti-foggant is used to prevent deterioration and conspicuous graininess.

The color antifoggant may be used in the emulsion layer itself, or may be used in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer which prevents deterioration of a dye image can be used in a color light-sensitive material using the silver halide emulsion of the present invention.

In order to prevent fogging due to discharge caused by charging of the photosensitive material to the hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention due to friction, etc., and to prevent deterioration of the image by ultraviolet light. It may contain an ultraviolet absorber.

The color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and / or an irradiation prevention layer.
In these layers and / or in the emulsion layer, a dye which flows out or is bleached from the color light-sensitive material during the development processing may be contained.

The silver halide emulsion layer of the silver halide light-sensitive material using the silver halide emulsion of the present invention and / or other hydrophilic colloid layer reduce the gloss of the light-sensitive material, enhance the writing property, and stick to each other between the light-sensitive materials. A matting agent can be added for the purpose of prevention.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of antistatic can be added to a light-sensitive material using the silver halide emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention, the coating property is improved,
Various surfactants are used for the purpose of antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion, and improvement of photographic properties (such as acceleration of development, hardening, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention is a photographic emulsion layer, the other layers are variter layer or α-olefrein polymer, laminated paper, flexible reflective support such as synthetic paper, cellulose acetate, It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid bodies such as glass, metal and pottery.

The silver halide material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, directly or (adhesiveness of the support surface, antistatic property, dimensional stability,
It may be applied via one or more subbing layers to improve wear resistance, hardness, antihalation, frictional properties, and / or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As the light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam, X-ray, Any known light source such as light emitted from a phosphor excited by γ rays or α rays can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 microsecond to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can form an image by performing color development processing known in the art.

The color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Further, these compounds are generally used in the color developer solution 1
About 0.1 g to about 30 g concentration, preferably color developer 1
Is used at a concentration of about 1 g to about 15 g.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include
N, N'-diethyl-p-phenylenediamine hydrochloride, N
-Methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-Hydroxyethylaminoaniline, 4-amiano-3-methyl-N, N'-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate And so on.

To the color developing solution applied to the processing of the silver halide photographic light-sensitive material of the present invention, known developer component compounds can be added in addition to the above-mentioned primary aromatic amine color developing agent.

For example, an alkali agent such as sodium hydroxide, sodium carbonate, potassium carbonate, an alkali metal sulfite salt, an alkali metal bisulfite salt, an alkali metal thiocyanate salt, an alkali metal halide, benzyl alcohol, a water softening agent and a thickening agent are optional. It can also be contained in.

The pH of the color developing solution is usually 7 or higher, most commonly about 10 to about 13.

The silver halide photographic light-sensitive material according to the present invention can contain these color developing agents as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and can be processed with an alkaline activating bath. The color-developing agent precursor is a compound capable of forming a color-developing agent under alkaline conditions, such as a shift base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a curser, a phosphoric acid amide derivative. Precursors, sugar amine reactant precursors, urethane type precursors may be mentioned. Precursors for these aromatic primary amine color developing agents are disclosed, for example, in U.S. Pat. Nos. 3,342,599 and 2,5.
07,114, 2,695,234, 3,719,492, U.S. Pat.No. 803,783, JP-A-53-185628, 54
−79035 publications, Research Disclosure Magazine 1
5159, 12146, and 13924.

It is necessary to add these aromatic primary amine color developing agents or their precursors so that a sufficient amount of color can be obtained only by the amount when activated. This amount varies greatly depending on the kind of the light-sensitive material, but it is generally between 0.1 and 5 mol, preferably 1 mol, per mol of silver halide.
It is used in the range of 0.5 mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. To incorporate in the photosensitive material, water,
It can also be dissolved in an appropriate solvent such as methanol, ethanol, acetone or the like, or added as an emulsion dispersion using a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. It can also be added by impregnating a latex polymer as described in Disclosure No. 14850.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as bleaching agents, among which iron (III), cobalt (III), copper (II)
Etc. Polyvalent metal compounds, especially complex salts of these polyvalent metal cations with organic acids, for example aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid. , Metal complex salts such as diglycolic acid and dithioglycolic acid, ferricyanates, dichromates, etc., alone or in an appropriate combination.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.

After the fixing process, a washing process is usually performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed, or both may be used in combination. The stabilizing solution used for the stabilizing treatment may contain a pH adjusting agent, a chelating agent, a fungicide, and the like. These specific conditions are described in JP-A-58-134,636.
You can refer to the official gazettes.

[Specific Effects of the Invention] As described above, the present invention provides a silver halide photographic light-sensitive material having good sensitivity and fog, excellent pressure resistance in both dry and wet states, and suitable for rapid processing. be able to.

[Specific Examples of the Invention] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Emulsion A) According to the method described in JP-A-59-48755, an aqueous solution containing potassium chloride and potassium bromide and an aqueous solution of silver nitrate were stirred vigorously in an inert gelatin aqueous solution at 50 ° C. A high silver chloride emulsion containing 2 mol% of silver bromide was obtained by simultaneously mixing for 60 minutes.

The pAg during mixing was controlled at 7.

When the characteristics of the obtained high silver chloride emulsion were measured according to the methods described above, the grains were high silver chloride grains having an average grain size of 0.8 μm and a coefficient of variation of 0.10. Further, the maximum density ratio (internal development / surface development) was measured according to the above-mentioned method and was found to be 1.2.
Then, washing with water for precipitation is carried out, and then sodium thiosulfate is added to the high silver chloride grains to carry out chemical sensitization. At the end of the chemical sensitization, the blue-sensitive sensitizing dye and stabilizing agent shown by the above-mentioned exemplified compound A-23 The agent was added to prepare a blue-sensitive high silver chloride emulsion.

(Emulsion B) Next, 30 minutes after the start of addition of an aqueous solution containing potassium chloride and potassium bromide and an aqueous solution of silver nitrate, silver halide 1
A high silver chloride emulsion having an average grain size of 0.8 μm, a coefficient of variation of 0.1 and a maximum density ratio of 1.3 was obtained in the same manner as Emulsion A except that 2 × 10 ⁻⁶ mol of K ₂ IrCl ₆ was added per mol. Further, a blue-sensitive high silver chloride emulsion was prepared in the same manner as the emulsion A.

(Emulsion C) An aqueous solution containing potassium bromide and potassium chloride and an aqueous solution of silver nitrate were mixed in an aqueous solution of inert gelatin with vigorous stirring at 70 ° C. for 120 minutes while controlling the pAg to 6 at the same time to obtain an average grain size of Diameter 0.8 μm,
A silver chlorobromide emulsion containing 90 mol% of silver bromide having a coefficient of variation of 0.11 and a maximum density ratio of 1.0 was obtained. A blue-sensitive silver bromide emulsion was prepared in the same manner as Emulsion A.

(Emulsion D) An aqueous solution containing potassium bromide and potassium chloride and an aqueous solution of silver nitrate were simultaneously added to an inert gelatin aqueous solution with vigorous stirring while controlling pAg to 7 at 50 ° C. Further successively, an aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added. The infusion time was 60 minutes. By this method, a high silver chloride emulsion containing 2 mol% of silver bromide, the outermost layer of which was a silver bromide phase, was obtained. The resulting emulsion had an average grain size of 0.8 μm, a coefficient of variation of 0.10 and a maximum density ratio of 1.2. Further, a blue-sensitive high silver chloride emulsion was prepared in the same manner as the emulsion A.

(Emulsion E) <Invention> Emulsion D except that 2 × 10 ⁻⁶ mol of K ₂ ICl ₆ per mol of silver halide was added 30 minutes after the start of the addition of an aqueous solution containing potassium bromide and potassium chloride and an aqueous solution of silver nitrate. The average particle size is 0.8 μm, coefficient of variation is 0.10,
A blue-sensitive high silver chloride emulsion having a maximum density ratio of 1.5 was prepared.

When this emulsion E was analyzed by an X-ray diffraction method, the peaks attributed to the high silver bromide phase showed a diffraction pattern which was clearly distinguishable from the peaks attributed to the high silver chloride phases other than the high silver bromide phase.

On the other hand, 80 g of yellow coupler as a high boiling organic solvent,
It is dissolved in a mixed solution of 30 g of dinonyl phthalate and 100 ml of ethyl acetate as a low boiling point organic solvent, 300 ml of 5% gelatin aqueous solution containing sodium dodecylbenzene sulfonate is added to this solution, and then dispersed in an ultrasonic homogenizer to disperse the yellow coupler. The dispersion was prepared.

Then, the following two layers were sequentially coated on the polyethylene-coated paper support from the support side to prepare silver halide photographic light-sensitive material samples 1 to 5. The addition amount shown below is the amount per 1 m ² unless otherwise specified.

Layer-1: 2.0 g gelatin, 0.3 g (silver equivalent) blue-sensitive silver halide emulsion ^* , 0.8 g yellow coupler, and
A layer containing 0.3 g of dinonyl phthalate.

Layer-2: 1.5 g of gelatin and the exemplified compound II-2
A layer containing a hardener shown in.

* Is shown in Table-1.

The evaluation method of the pressure characteristics is as follows.

[Dry Pressure Property] A ball point needle having a sphere diameter of 0.1 mm was erected vertically on the sample surface, and the sample surface was translated at a speed of 1 cm / sec while a load was applied to the ball point needle at the same time.

After that, each sample was subjected to stepwise exposure with white light using a sensitometer (KS-7 type manufactured by Konishi Rokusha Kogyo Co., Ltd.),
Processing is performed according to the following processing steps, and the color density of the part where pressure is applied and the part where pressure is not applied in the vicinity of the color density of about 0.3 is measured by the Sakura Micro Densitometer (PD
M-5) was measured and the following evaluations were performed. In this case ΔD
^The smaller the ^D value, the better the pressure resistance.

ΔD ^D = (concentration of the part where pressure is applied)-(concentration of the part where pressure is not applied) [Pressure characteristic at the time of wetting] After subjecting each sample to the stepwise exposure as described above,
After immersing in pure water for 3 minutes, a ball-point needle with a spherical shape of 0.3 mm stands vertically on the wet sample surface, and the sample surface is 1 cm / se.
A parallel load was applied to the ball point needle while translating at the speed of c. The treatment was performed according to the treatment steps shown below, and the color density of the pressure-applied portion and the non-pressure-applied portion of the color density of about 0.3 was measured with a Sakura Microdensitometer (PDM-5). I did. In this case, the smaller the ΔD ^W value, the better the pressure resistance.

ΔD ^W = (concentration of a portion under pressure)-(concentration of a portion without pressure) Table 1 shows the results obtained above.

[Processing process] Temperature Time Color development 34.7 ± 0.3 ℃ 50 seconds Bleach-fixing 34.7 ± 0.5 ℃ 50 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds [Color developer] Pure water 800ml Ethylene glycol 10 ml N, N-diethylhydroxylamine 10 g Potassium chloride 2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5 g Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g Optical brightener ( 4,4'-Diaminostilbenedisulfonic acid derivative) 1g Add water to adjust the total amount to 1 and adjust to pH 10.08.

(Bleaching fixer) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust pH to 7.1 with potassium carbonate or glacial acetic acid and water Is added to bring the total amount to 1.

(Stabilizing Solution) 5-Chloro-2-methyl-4-isothiazolin-3-one 1g 1-Hydroxyethylidene-1,1-diphosphonic acid 2g Water was added to 1 and the pH was adjusted with sulfuric acid or potassium hydroxide. Adjust to 7.0.

The following can be found from Table-1. It can be seen from Samples 1 and 3 that the high silver chloride emulsion is significantly inferior in pressure resistance to the silver chlorobromide emulsion. Further, from Samples 2 and 4, the combination of high silver chloride grains and metal ions or the emulsion of the present invention alone containing no metal ion showed almost no improvement in pressure resistance, whereas Sample 5 having the constitution of the present invention The pressure resistance is remarkably improved and the object of the present invention is achieved.

Further, samples 3 and 5 were exposed and processed in the same manner as the evaluation of pressure resistance. However, here, the processing time with the color developing solution was changed to 30 seconds, 50 seconds, 90 seconds, and 210 seconds. The sensitivity and the maximum density of each sample obtained by the treatment were measured with an optical densitometer (PDA-60, manufactured by Konishi Roku Photo Co., Ltd.). The obtained results are shown in Table-2.

From Table-2, Sample 5 using the high silver chloride emulsion was 30 seconds to 50 seconds.
The maximum sensitivity and the maximum density are reached by the second, whereas the development progress is remarkably slow in Sample 3 using the silver chlorobromide emulsion, and the sensitivity and the maximum density are only about half that of silver chloride. I understand. The same test was performed on Samples 1, 2, and 4 and similar results were obtained.

Example-2 The following blue-sensitive high silver chloride emulsion was prepared in the same manner as in Emulsion E of Example-1.

Emulsion F Same as Emulsion E except that it contains 5 × 10 ^-6 mol of cadmium per mol of silver halide Emulsion G Same as Emulsion H except that it contains 5 × 10 ^-5 mol of rhodium per mol of silver halide Emulsion H Same as Emulsion E, except that the outer layer was a high silver chloride emulsion containing 5 mol% of silver bromide composed of a silver chlorobromide phase containing 80 mol% of silver bromide. Example,
Similar to Sample 5 of No. 1, it showed good pressure resistance in dry and wet.

Further, the rapid processing suitability was evaluated in the same manner as in Example-1, and as in the case of Sample 5 in Example-1, excellent rapid processing suitability was shown.

However, the sensitivity was slightly lower than that of K ₂ IrCl ₄ used in Example-1.

Example-3 The following emulsions were prepared in the same manner as in Example-1.

(Emulsion I) A green light-sensitive high silver chloride emulsion using the above-indicated compound B-4 containing 3 mol% of silver bromide having an average grain size of 0.5 μm, a coefficient of variation of 0.12 and a maximum density ratio of 1.5 in the same manner as emulsion A. .

(Emulsion J) Same as Emulsion E and Emulsion I, green containing 3 mol% of silver bromide having an average grain size of 0.5 μm, a coefficient of variation of 0.11 and a silver bromide phase in the outermost layer having a maximum density ratio of 1.8. Photosensitive high silver chloride emulsion.

(Emulsion K) A red-sensitive high silver chloride emulsion similar to emulsion I except that the exemplified compound C-9 was used.

(Emulsion L) Red-sensitive highly chlorinated silver emulsion of the present invention similar to Emulsions J and K.

Overlay samples were prepared with the configurations shown in Tables 3 and 4. These samples were evaluated for pressure resistance as in Example-1. However, the exposure shall be separation exposure of blue, green, and red light, and the densities of cyan, magenta, and yellow shall be D _R ,
These are D _G and D _B. The obtained results are shown in Table-5.

Further, the color development time was changed and evaluated in the same manner as in Example-1. The obtained results are shown in Table-6.

Hardener II-2 7mg / g Gelatin However, in Sample No. 31, 50 mg of the exemplified compound I-12 represented by the general formula [I] was added to each layer per mol of silver halide.

As can be seen from Table-5, Samples 31 and 32 having the constitution of the present invention show excellent pressure resistance as in Examples-1 and 2 even when they are laminated. Further, from Sample 31, the mercapto compound represented by the general formula [I] preferably used in the present invention has improved pressure resistance when added to the constitution of the present invention, and brings about preferable results.

Further, it can be seen from Table 6 that the high chloride silver halide emulsion of the present invention has a remarkably fast color developing property even in the case of multiple layers.

Preparation of Example-4 (Emulsion M) An emulsion having a high silver chloride content and a high iridium content on the grain surface side was prepared based on the method for producing EM-2 disclosed in JP-A-61-47941.

Contains silver nitrate (Ag1) and sodium chloride, sodium bromide and potassium iodide in a molar ratio of 9.5: 90: 0.5, and Ag
An aqueous solution containing 1.3 × 10 ^-7 mol of K ₂ IrCl ₆ per mol of silver of 1 was vigorously stirred in an inert gelatin solution to obtain a pH of 3,
It was added at the same time while keeping at Ag7.

Next, silver nitrate (Ag2), which is 5 times the molar amount of Ag1, sodium chloride and potassium iodide in a molar ratio of 99.5: 0.5, and Ag2
An aqueous solution which was equimolar with 1.3 × 10 ^-6 mol of K ₂ IrCl ₆ per 1 mol of Ag 2 silver was simultaneously added.

It was washed with dechlorinated water and then sensitized in the same manner as Emulsion E of the present invention. The obtained particles have an average particle size of 0.8 μm and a coefficient of variation of 0.1.
Was 3. The contents are shown in the table below.

Emulsion M is the sample N of Example 1 of JP-A-61-47941.
It has the same composition as the particles used in o.10.

Using Emulsion E and Emulsion M of the present application, evaluation was performed in the same manner as in Example 1 of the present application.

As is apparent from the above table, the emulsion of the present invention is superior in pressure characteristics and development progress.

As described above, the constitution of the present invention has made it possible to provide a silver halide light-sensitive material for rapid processing, which is an object of the present invention and is excellent in pressure resistance in both a dry state and a wet state.

 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-58-95736 (JP, A) JP-A-58-125612 (JP, A) JP-A-60-162246 (JP, A) JP-A 61- 47941 (JP, A) JP 56-147142 (JP, A) JP 58-211142 (JP, A) JP 61-67845 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one layer of the silver halide emulsion layer is 10 ^-8 to 10 per mol of silver halide. ^-5 silver halide photographic light-sensitive material containing high silver chloride grains having a silver chloride content of 80 to 99 mol% in which a metal ion and a high silver bromide-containing phase are localized outside the grain material.