JPH06317861A - Production of silver halide emulsion - Google Patents

Abstract

PURPOSE:To provide a producing method for a silver halide emulsion having high sensitivity, high contrast and high coloring density and excellent in pressure resistance. CONSTITUTION:In the method for producing the silver halide emulsion by applying chemical aging in the presence of a spectral sensitizing dyestuff after forming particles of the silver halide emulsion, the silver halide emulsion is composed of normal crystal silver halide particles >=60% in average ratio of (100) plane in the total particles and the spectral sensitizing dyestuff is added at >=25 deg.C to <=50 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide emulsion, and more specifically, a method for producing a silver halide emulsion comprising spectrally sensitized normal crystal silver halide grains having a high (100) face ratio. It is about.

[0002]

2. Description of the Related Art In recent years, silver halide color photographic light-sensitive materials have not only high sensitivity and high image quality but also resource saving,
For the purpose of cost reduction and low replenishment of processing solution, an emulsion having a high coloring density is required even with a small amount of silver.

Silver halide emulsions include cubes, octahedra,
Emulsions having various outer shapes such as normal crystal emulsions such as tetradecahedral and rhombodecahedral, and twinned emulsions including double twins such as tabular grains are known.

Among them, a tabular grain which is a twinned emulsion has a small light scattering due to its outer shape and a large specific surface area.
Since a large amount of sensitizing dye can be used and the spectral sensitization efficiency is high, it has been used as a highly sensitive commercial light-sensitive material.

On the other hand, a normal crystal emulsion can be monodispersed relatively easily due to its isotropic structure, and uniform spectral sensitization and chemical sensitization (chemical ripening) can be performed among grains. It is expected to be an emulsion suitable for the purpose of providing an emulsion having a high tone and a high color density, because it has characteristics such as being able to be obtained.

Typical of normal crystal emulsions are cubic emulsions whose surface is composed of (100) faces and octahedral emulsions whose surface is composed of (111) faces. Various basic researches have been conducted on these two emulsions since ancient times.
photogr. Sci. Eng. , 18, 215-22
5 (1974), a cubic emulsion having a (100) face has a smaller intrinsic desensitization when adsorbing a sensitizing dye than an octahedral emulsion, and the cubic emulsion has a color It may be excellent as a sensitized emulsion.

Japanese Unexamined Patent Publication No. 61-205929 discloses a method for producing an emulsion having high color sensitization sensitivity with normal crystal grains having a high (100) face ratio by devising a method for adding a sensitizing dye. Therefore, it seems that the advantages of the cubic emulsion described above are utilized.

It is not limited to cubic emulsions that the addition of a sensitizing dye, particularly the chemical sensitization of silver halide grains in the presence of a sensitizing dye, not only enhances the adsorption of the sensitizing dye but also , A technology effective in obtaining highly sensitive and storable color sensitized grains by controlling chemical sensitization (chemical ripening) and reducing the intrinsic desensitization of silver halide grains caused by color sensitization Is known to be. These are disclosed in, for example, JP-A Nos. 55-26589, 61-103149 and 61-133941.

When such a technique is applied to a cubic emulsion, a high color sensitizing sensitivity can be certainly achieved, but it has a drawback that the gradation is still insufficient and the pressure resistance is poor.

Various pressures are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example,
The negative film for general photography is bent or pulled for frame advance when it is rolled up in a cartridge or mounted on a camera.

On the other hand, a sheet-shaped film such as a photosensitive material for printing or a direct medical roentgen photosensitive material is often bent or bent because it is directly handled by a person.

Further, all photosensitive materials are subjected to great pressure during cutting and processing.

As described above, when various pressures are applied to the photographic light-sensitive material, pressure is applied to the silver halide grains by using gelatin as a holder (binder) of silver halide grains or a plastic film as a medium as a medium. It is known that when a pressure is applied to the silver halide grains, the photographic properties of the photographic light-sensitive material are changed. B. Mat
her, J .; Opt. Soc. Am. , 38.1054
(1948), p. F. aelens and P.A. d
e Smet. Sci. et Ind Photo. , 2
5. No. 5.178 (1954), p. Faelen
s. J. Photo. Sci. 2.105 (1954).

It has been found by the study of the present inventors that the increase in fog particularly when a pressure is applied is exacerbated by the devised method of adding the sensitizing dye.

In JP-A-5-80445, a sensitizing dye is added at a relatively low temperature and then chemically ripened at a higher temperature to obtain a high-contrast, high-contrast emulsion for a few minutes after exposure. A method for producing an emulsion having excellent latent image stability in the very early period is disclosed. However, the emulsion described here is an emulsion containing a silver chloride content of 90 mol% or more, and silver chloroiodobromide and silver iodobromide having a low silver chloride content usually used for photographic light-sensitive materials are not used. No mention is made of the crystalline phases such as cubes and octahedra.

Further, the pressure characteristic is not discussed at all.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a silver halide emulsion having high sensitivity, high contrast, high color density and excellent pressure resistance.

[0018]

The above objects of the present invention have been achieved by the following methods (1) to (5) for producing a silver halide emulsion.

(1) In the method for producing a silver halide emulsion, which comprises chemically ripening the silver halide emulsion in the presence of a spectral sensitizing dye after forming the grains, the silver halide emulsion has an average of all grains ( 100) A method for producing a silver halide emulsion which is an emulsion composed of normal-crystal silver halide grains having an area ratio of 60% or more, and in which the spectral sensitizing dye is added at a temperature of 25 ° C or higher and 50 ° C or lower.

(2) The method for producing a silver halide emulsion according to the above (1), wherein the amount of the spectral sensitizing dye added is 2% or more and 25% or less of the saturated coverage of the silver halide emulsion.

(3) The method for producing a silver halide emulsion as described in (1) above, wherein the normal silver halide grains have an average silver iodide content of 0.5 mol% or more and 7 mol% or less.

(4) The method for producing a silver halide emulsion as described in (1) above, wherein the normal crystal silver halide grains are sensitized with selenium.

(5) The method for producing a silver halide emulsion according to the above (1), wherein the spectral sensitizing dye is a cyanine dye.

The present invention will be described in more detail below.

First, the spectral sensitization and the spectral sensitizer in the production method of the present invention will be described below.

It is essential that the step of chemically sensitizing the emulsion of the present invention includes a step performed in the presence of a spectral sensitizing dye. However, the case where the chemical sensitization is terminated by adding the spectral sensitizing dye is also included in the above step. The end of chemical sensitization refers to the stage at which the progress of chemical sensitization has stopped.

The spectral sensitization referred to in the present invention can be carried out at any stage of emulsion preparation known to be useful so far, before the completion of chemical ripening. Spectral sensitization can occur concurrently with chemical sensitization, as taught in US Pat. Nos. 3,628,960 and 4,225,666, or can precede chemical sensitization altogether. Further, it is also possible to start the spectral sensitization before the completion of the silver halide grain precipitation. It is also possible, as taught in US Pat. No. 4,225,666, to have some of the spectral sensitizing dyes be present in the process prior to the completion of chemical sensitization and the balance introduced after chemical sensitization. .

That is, the spectral sensitizing dye is
During grain formation, during physical ripening, may be added in any step before the water washing step, and also before chemical sensitization, during chemical sensitization,
It may be added at any time immediately before the end of chemical sensitization.

The addition temperature of the spectral sensitizing dye in the present invention is essential to be in the range of 25 ° C to 50 ° C, preferably 30 ° C to 45 ° C.

If the addition temperature exceeds 50 ° C., the sensitivity becomes difficult to increase and the merit of the spectral sensitizing dye cannot be fully utilized, which is not preferable.

The spectral sensitizing dye is usually added in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, but the specific surface area varies depending on the emulsion grain size. The amount of addition also changes accordingly. Therefore, in the present invention, it is defined as a percentage when the saturated coverage of the emulsion with respect to the spectral sensitizing dye is 100%. According to this regulation, 2% of the saturated coating amount is used in the present invention.
It is more than 80% and preferably less than 50%,
The following is more preferable. Furthermore, 25% or less is preferable,
Most preferably, it is 15% or less. If the addition amount is less than 2%, the sensitivity is significantly lowered, and if it exceeds 80%, the development suppression becomes large and the image becomes soft.

Since the saturated coating amount depends on the size of the spectral sensitizing dye and the silver halide emulsion and the (100) plane ratio, it must be determined in the combination of the spectral sensitizing dye and the silver halide emulsion used. Saturation coverage is Jo
urnal of Image Science, Vo
l. 29,165 (1985).

In the present invention, p when the spectral sensitizing dye is added
Although H and pAg can be experimentally determined by the characteristics of the emulsion and the characteristics of the dye, it is preferable to select pH in the range of 5 to 8 and pAg in the range of 6 to 9.5.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. A particularly preferred dye is a cyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes.
That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and After the aromatic hydrocarbon ring is fused to these nuclei, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzine Imidazole nucleus and quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,288,545.
977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964,
No. 3,666,480, No. 3,672,898
No. 3,679,428, No. 3,703,37
No. 7, No. 3,769, 301, No. 3, 814, 6
No. 09, No. 3,837,862, No. 4,026.
707, British Patents 1,344,281 and 1,
No. 507,803, Japanese Patent Publication No. 43-4936, No. 53-
No. 12375, JP-A Nos. 52-110618 and 52-
No. 109925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

As a method for adding a sensitizing dye to the above photographic emulsion, various methods conventionally proposed can be applied. For example, as described in US Pat. No. 3,469,987, a sensitizing dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. Good. Still further, the sensitizing dyes of the present invention can be individually dissolved in the same or different solvents, and these solutions can be mixed or added separately before being added to the emulsion.

In the present invention, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol or acetone can be used as a dye solvent when the sensitizing dye is added to the silver halide emulsion.

Next, the normal crystal silver halide grains and selenium sensitization of the present invention will be described below.

The normal crystal grains of the present invention are grains in which the average (100) plane area ratio of all grains on the surface of all grains is 60% or more. These usually exhibit the shape of a cube. In addition, corners and overhangs may be lacking or rounded due to the coexistence of other surfaces such as the (111) surface and the (110) surface.

More preferably, the average (100) face ratio is 8
0% or more of the particles, more preferably a surface ratio of 90
%, More preferably 100% face ratio, more complete cubic grains.

As a method of measuring the surface ratio of the normal crystal grains, an X-ray diffraction method utilizing the orientation of the grains or a Kubelka-Munk (utilizing the absorption spectrum of the sensitizing dye adsorbed on the silver halide grains is used. Tadaaki Tani,
Known methods such as the method described in The Chemical Society of Japan, page 942, 1984) can be used.

The normal crystal grains used in the present invention are preferably chemically sensitized with a selenium compound, so-called selenium sensitization.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. Usually, the unstable selenium compound and / or the non-unstable selenium compound is used by adding it and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound,
For example, Japanese Patent Publication Nos. 44-15748 and 48-13489.
It is preferable to use the compounds described in JP-A Nos. 4-25832 and 4-112172.

Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate),
Selenoureas, selenoketones, selenoamides, selenocarboxylic acids (eg, 2-selenopropionic acid, 2
-Selenobutyric acid), selenoesters, diacyl selenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium.

Although the preferred types of labile selenium compounds have been described above, these are not limiting. When it comes to unstable selenium compounds as sensitizers for photographic emulsions, the structure of the compounds is not so important as long as selenium is unstable, and the organic part of the selenium sensitizer molecule carries selenium. It is generally understood by those skilled in the art that it has no role except to make it present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

The non-unstable selenium compound used in the present invention is, for example, Japanese Patent Publication Nos. 46-4553 and 52-344.
The compounds described in No. 92 and No. 52-34491 are used. As the non-unstable selenium compound, for example,
Selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethiones, and these Examples include derivatives.

Of these selenium compounds, preferred are compounds represented by the following formulas (I) and (II).

[0049]

[Chemical 1] In formula (I), Z ₁ and Z ₂ may be the same or different, and are an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl). ), An aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), a heterocyclic group (eg, ,
Pyridyl, thienyl, furyl, imidazolyl), -NR
₁ (R _2), - represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl,
4-trifluoromethylbenzoyl).

In formula (I), preferably Z ₁ represents an alkyl group, an aryl group or --NR ₁ (R ₂ ), and Z ₂ represents --NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R ₆
May be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

Formula (I) is more preferably N, N-dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

[0053]

[Chemical 2] In the formula (II), Z ₃ , Z ₄ and Z ₅ may be the same or different, and an aliphatic group, an aromatic group, a heterocyclic group,
-OR ₇ , -NR ₈ (R ₉ ), -SR ₁₀ , -SeR ₁₁ ,
X represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈
And R ₉ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom.

In the formula (II), Z ₃ , Z ₄ , Z ₅ and R
_The aliphatic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group (for example, methyl, ethyl, n-propyl). , Isopropyl, t-butyl, n-
Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the formula (II), Z ₃ , Z ₄ , Z ₅ and R
_The aromatic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (eg, phenyl,
Pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the formula (II), Z ₃ , Z ₄ , Z ₅ and R
_7, a heterocyclic group represented by R _8, R _9, R ₁₀ and R _11, the nitrogen atom, a 3- to 10-membered ring containing at least one of an oxygen atom or a sulfur atom, a saturated or unsaturated heterocyclic Represents a ring group (eg, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In formula (II), R ₇ , R ₁₀ and R ₁₁
The cation represented by represents an alkali metal atom or ammonium. The halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the formula (II), preferably Z ₃ and Z
₄ or Z ₅ represents an aliphatic group, an aromatic group or -OR _7, R ₇ represents an aliphatic group or an aromatic group.

Formula (II) more preferably represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate.

Specific examples of the compounds represented by the formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0062]

[Chemical 3]

[0063]

[Chemical 4]

[0064]

[Chemical 5]

[0065]

[Chemical 6]

[0066]

[Chemical 7]

[0067]

[Chemical 8]

[0068]

[Chemical 9]

[0069]

[Chemical 10] These selenium sensitizers are dissolved in water or an organic solvent such as methanol and ethanol, alone or in a mixed solvent, and added at the time of chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. The combined use of an unstable selenium compound and a non-unstable selenium compound is preferable.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably, it is 1 × 10 ⁻⁷ mol or more,
Moreover, it is 1 × 10 ⁻⁴ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, with respect to pH, the effect of the present invention can be obtained in a wide range of 4 to 9.

The selenium sensitization can be achieved more effectively by performing it in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,62
No. 8, JP-A Nos. 54-1019 and 54-158917.
(A) organic thioethers described in JP-A Nos. 58-82408, 55-77737 and 55.
-2982 (b) thiourea derivative, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom (c) described in JP-A-53-144319. (D) imidazoles, (e) sulfites described in JP-A-54-100717,
(F) Thiocyanate.

As a particularly preferred silver halide solvent,
There are thiocyanates and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more per 1 mol of silver halide, and 1 × 10 ^−2.
It is less than or equal to mol.

The emulsion of the present invention is preferably combined with sulfur sensitization and gold sensitization in chemical sensitization.

Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

For the sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine. Others, for example, US Pat.
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-2493.
No. 7, and sulfur sensitizers described in JP-A-55-45016 can also be used. The amount of sulfur sensitizer added is
The amount is sufficient to effectively increase the sensitivity of the emulsion.
This amount will vary over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc.
1 x 10 ^-7 mol or more, 5 x 10 per mol of silver halide
^-4 mol or less is preferable. The molar ratio with the selenium sensitizer is arbitrary, but it is desirable to use the sulfur sensitizer in an equimolar amount or more to the selenium sensitizer.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include, for example, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and pyridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 per mol of silver halide.
It is preferably not less than 5 mol and not more than 5 × 10 ⁻⁴ mol.

At the time of chemical ripening, there is no particular limitation on the timing and order of addition of the silver halide solvent, the selenium sensitizer, the sulfur sensitizer and the gold sensitizer. ) Or during the course of chemical ripening, the above compounds can be added at the same time or at different addition points. In addition, upon addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone, and then added.

The normal crystal silver halide grains used in the present invention are silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. The preferred average silver iodide content varies depending on the intended light-sensitive material. For example, 0.1 to 1 for X-ray sensitive material
A preferable range is 5 mol%, and for graphic arts and micro sensitive materials, 0.1 to 5 mol%. In the case of a photographic light-sensitive material represented by a color negative, it is preferably 0.1 to 2
A silver halide containing 0 mol% of silver iodide, more preferably 0.20 to 10 mol%, particularly preferably 0.5.
~ 7 mol%. It is preferable that the silver iodobromide grains contain silver chloride in order to reduce lattice strain. If the average silver iodide content is too high, it becomes difficult to prepare a cubic emulsion and it is difficult to form a hard emulsion.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. The typical one is Japanese Patent Publication No. 43-13.
162, JP-A-61-215540 and 60-22.
No. 2845, No. 60-143331, No. 61-753
Nos. 37 and the like are core-shell type or double structure type grains having a halogen composition in which the inside and the surface layer of the grains are different. Further, it is not a simple double structure but a triple structure as disclosed in JP-A-60-222844 or a multilayer structure having more than that, or a different composition on the surface of the core-shell double structure particles. It is possible to thinly apply a silver halide having.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be prepared. Examples of these are JP-A-59
-133540, 58-108526, European Patent 199,290A2, JP-B-58-24772,
It is disclosed in JP-A-59-16254. The crystal to be bonded can be generated by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, (100) plane and (1
This is the case where the halogen composition is changed only on one surface of the tetrahedral grain 11), or on one of the main plane and the side surface of the tabular grain.

It is preferable that the normal crystal grains of the present invention contain dislocations. It is possible to observe dislocation lines in a normal crystal grain with a transmission electron microscope. It is possible to select dislocations or curved dislocations introduced linearly with respect to a specific direction of the crystal orientation of the particles, and to introduce the dislocations throughout the particle or only in a specific part of the particle, for example, the fringe of the particle. The dislocation can be introduced only in a portion or a vertex.

The silver halide emulsion used in the present invention can be processed by a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1.
Alternatively, the surface may be modified as disclosed in West German Patent No. 2,306,447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases that the unevenness is intentionally formed.
A method of forming a hole in a part of the crystal described in JP-A-58-106532 and 60-221320, for example, a vertex or a center of a plane, or US Pat.
Raffle particles described in 3,966 are an example.

The grain size of the emulsion used in the present invention can be evaluated by the diameter corresponding to the circle of the projected area using an electron microscope or the diameter corresponding to the sphere of the volume measured by the Coulter counter method. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less and coarse particles having a diameter of more than 2 microns. Grains having a size of 0.06 micron or more and 1 micron or less are preferably used as the photosensitive silver halide grains, and more preferably grains having a size of 0.06 micron or more and 0.5 micron or less are used.

The emulsion used in the present invention is preferably a monodisperse emulsion having a narrow size distribution. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and further preferably 15% or less.

In some cases, the monodisperse emulsion is defined as a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of number of grains or weight. In order to satisfy the target gradation of the light-sensitive material, the emulsion layers having substantially the same color sensitivity have different grain sizes.
One or more kinds of monodisperse silver halide emulsions can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

A method of adding silver halide grains which have been preliminarily formed into a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Are optionally preferred. These can be used as seed crystals, and are effectively supplied as silver halide for growth. In the latter case,
It is preferable to add an emulsion having a small grain size, and as an addition method, the whole amount may be added at once, divided into a plurality of times, or continuously added. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method of converting most or a very small part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,498.
142,900, European Patents 273,429, 273,430 and West German Published Patent 3,819,24.
It is disclosed in No. 1 and the like and is an effective particle forming method.
A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

In addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in No. 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
No. 3, ibid. 3,342, 605, ibid. 3, 415, 65
No. 0, No. 3,785,777, West German Published Patent No. 2,
It can be selected and used from the methods described in Nos. 556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used.
The total amount of these ripening agents can be mixed in the dispersion medium in the reactor before adding the silver and halide salts, or the halide salt, silver salt or peptizer can be added together with the reactor. It can also be introduced inside. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agent, for example, ammonia, thiocyanates (eg, rhodan potassium, rhodan ammonium), organic thioether compounds (eg, US Pat. Nos. 3,574,628, 3,021,215, and No. 3,057,724, No. 3,038,805,
No. 4,276,374, No. 4,297,439
No. 3,704,130, No. 4,782,01
3, compounds described in JP-A-57-104926, etc.) and thione compounds (for example, JP-A-53-82408).
No. 55-77737, U.S. Pat. No. 4,221,8.
No. 63, etc., the compounds described in JP-A No. 53-144319), and the mercapto compounds (the silver halide grains described in JP-A No. 57-202531). A mercapto compound that can promote) and an amine compound (for example, JP-A-54-
No. 100717).

It is advantageous to use gelatin as a protective colloid used when preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and redispersed with newly prepared gelatin. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

When the emulsion of the present invention is prepared, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, it is preferably added after grain formation and before chemical sensitization when the grains are formed, when the grains are modified or when they are used as chemical sensitizers. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Examples of the metal include Mg,
Ca, Sr, Ba, Al, Sc, Y, La, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ga, Ru, R
h, Pd, Re, Os, Ir, Pt, Au, Cd, H
g, Tl, In, Sn, Pb and Bi can be used. These metals may be in the form of salts that can be dissolved at the time of grain formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, and hexacoordinated complex salts. Can be added. For example, CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3)
₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ Ir
Cl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) ₆
Is mentioned. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. Aqueous hydrogen halide solution (eg HCl, HBr) or alkali halide (eg KCl, NaCl, KBr, NaB) to stabilize the solution.
The method of adding r) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (eg AgN
O ₃ ) or an alkali halide aqueous solution (eg Na
Cl, KBr, KI) and continuously added during the formation of silver halide grains. Furthermore, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of 1 to 7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salt,
Ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol per 1 mol of silver halide is suitable.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth.
It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to exchange it for silver ions. Particularly effective is a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions. The silver ions formed here may form a sparingly water-soluble silver salt such as silver halide, silver sulfide or silver selenide, or a silver salt easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone,
Hydrogen peroxide and its adducts (eg NaBO ₂ · H
₂ O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na _{4
P 2 O 7 · 2H 2 O} 2, 2Na 2 SO 4 · H 2 O 2 · 2
H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ , K
₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ) and peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O,
4K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H ₂ O,
Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] .6H ₂ O),
Oxygenates such as permanganates (eg KMnO ₄ ), chromates (eg K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate). ), High valent metal salts (eg potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidant, for example, p-
Examples thereof include quinones such as quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B).

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone type organic oxidizing agents.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected and used from the method of performing reduction sensitization after using an oxidizing agent, the reverse method, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) A number of compounds known as antifoggants or stabilizers, such as chitraazaindenes), pentaazaindenes, can be added. For example, those described in U.S. Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One of the preferable compounds is JP-A-63-212.
There are compounds described in No. 932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Addition during emulsion preparation to exert the original antifogging and stabilizing effects, in addition to controlling the crystal habit of grains, reducing the grain size, reducing the solubility of grains, controlling chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

When the emulsion produced according to the method of the present invention is used in a color photographic light-sensitive material, the layer structure is such that a silver halide of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer is formed on a support. It suffices that at least one of the emulsion layers is provided, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, couplers such as those described in JP-A No. 61-20038, DIR compounds and the like may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. The constitution of two layers of the sensitivity emulsion layer can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support,
Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest photosensitivity, the middle layer is the silver halide emulsion layer having a lower photosensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, BL, GL, RL
It is preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer, adjacent to or adjacent to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide that can be used together when the silver halide grains of the present invention are used in a photographic light-sensitive material will be described below.

A preferred silver halide which can be used in combination in the photographic emulsion layer of the photographic light-sensitive material is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. is there. Particularly preferred is about 2 mol% to about 10 mol%
Up to silver iodobromide or silver iodochlorobromide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large size grains having a projected area diameter of up to about 10 μm, and it may be a polydisperse emulsion or a monodisperse emulsion. Good.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and "Graphide's Physics and Chemistry" by Graphide, published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628, 3,655,364 and British Patent 1,413,7.
Monodisperse emulsions described in No. 48 and the like are also preferable.

Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, 4,439,520
No. 2,112,157 and the like, and can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which grains are formed, or a type having a latent image on both the surface and the inside, but a negative type. It is necessary to be an emulsion of. In the case of an internal latent image type emulsion, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-133.
No. 542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used.
The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

For the photographic light-sensitive material, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The obtained silver halide grains and colloidal silver can be preferably used for the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain in which the inside or the surface of the grain is fogged is described in US Pat. No. 4,626,498.
And JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. Examples of the silver halide having a fogged grain interior or surface include silver chloride, silver chlorobromide, silver iodobromide,
Any of silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.
75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse emulsions (the weight of silver halide grains or the number of grains is at least 9).
5% has a particle size within ± 40% of the average particle size).

For the photographic light-sensitive material using the emulsion prepared according to the method of the present invention, it is preferable to use non-light-sensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating solution, for example, a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound may be added in advance. preferable. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

[0139] The silver coating amount of photographic light-sensitive material using the created emulsion according to the method of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23-24 page 648 right column-866-868 page Supersensitizer 649 page right column 4 brightener page 24 647 page right column 868 page 5 antifoggant, page 24 to 25 page 649 right column 868 to 870 stabilizer 6 light absorber, page 25 to 26 Page 649 Right column to page 873 Filter dye, page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column Page 650 Left column to page 872 Right column 8 Dye image stabilizer page 25 650 Page left column Page 872 9 Hard film Agents Page 26 651 Left column 874 to 875 Page 10 Binder page 26 651 Page left column 873 to 874 Page 11 Plasticizer and lubricant page 27 650 Page right column 876 Page 12 Coating aid, Page 26 to 650 page 650 Right column 875 to 876 Surfactant 13 Antistatic agent Page 27 650 Page 850 Right column 876 to 877 Page 14 Matting agent 878 to 879 To prevent deterioration of photographic performance due to formaldehyde gas, It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503.

Further, a photographic light-sensitive material using an emulsion prepared according to the method of the present invention is described in US Pat. No. 4,740,4.
54, No. 4,788,132, JP-A-62-18.
539 and the mercapto compounds described in JP-A 1-283551 are preferably contained.

Further, the compounds described in JP-A No. 1-106052, which contain a fog-generating agent, a development accelerator, a silver halide solvent or a precursor thereof, irrespective of the amount of developed silver produced by the development processing, are contained. Preferably.

Further, international publication WO88 / 04794,
Dyes dispersed by the method described in JP-A-1-502912, or EP317,308A, US Pat.
It is preferable to incorporate the dyes described in JP-A Nos. 420,555 and 1-259358.

Various color couplers can be used in the color photographic light-sensitive material using the emulsion prepared according to the method of the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferred, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include pheno type and naphthol type couplers. US Pat.
No. 2,212, No. 4,146396, No. 4,22
No. 8,233, No. 4,296,200, No. 2,3
69,929, 2,801,171, 2,
772, 162, 2, 895, 826, 3,772,002, 3,758,308, 4,334,011, 4,327,173,
West German Patent Publication No. 3,329,729, European Patent No. 12
No. 1,365A, No. 249,453A, U.S. Pat. No. 3,446,622, No. 4,333,999, No. 4,775,616, No. 4,451,559,
No. 4,427,767, No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, and those described in JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and 64-554.
Nos. 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,818,67.
The imidazole coupler described in No. 2 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color-forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds which release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, Item VII-F and No. 307105,
Patents described in paragraph VII-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

In addition, R. D. No. 11449, same N
o. The bleaching accelerator releasing couplers described in JP-A No. 24241 and JP-A No. 61-201247 are effective for shortening the processing time of a bleaching-capable processing step. In particular, when added to a light-sensitive material using the above-mentioned tabular silver halide grains,
The effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, and JP-A-59-157638 and 59-170840. Those described in No. 10 are preferable. In addition, JP-A-60-10702
No. 9, 60-252340, and JP-A 1-44940.
The compounds described in JP-A No. 1-45687, which release a fogging agent, a development accelerator, a silver halide solvent and the like by a redox reaction with an oxidized product of a developing agent are also preferable.

In addition, when the emulsion produced according to the method of the present invention is used in a color photographic light-sensitive material, compounds usable in the invention include, for example, competitive couplers described in US Pat. No. 4,130,427 and US Pat. 4,283,47
No. 2, No. 4,338,393, No. 4,310,6
No. 18, etc., multi-equivalent couplers, JP-A-60-185.
950, DIR described in JP-A-62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
Nos. 73,302A and 313,308A, which release dyes that restore color after withdrawal, and US Pat.
Examples thereof include ligand releasing couplers described in U.S. Pat. No. 555,477, couplers releasing a leuco dye described in JP-A-63-75747, and couplers releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

The coupler used in the light-sensitive material can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include, for example, phthalic acid esters (for example, dibutyl phthalate,
Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t
ert-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-te)
rt-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). Moreover, as an auxiliary solvent,
Boiling point is about 30 ° C or higher, preferably 50 ° C or higher and about 160 ° C
The following organic solvents and the like can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,27
No. 4 and No. 2,541,230.

In the color light-sensitive material using the emulsion prepared according to the method of the present invention, phenethyl alcohol and those described in JP-A Nos. 63-257747, 62-272248, and 1-80941 are used. For example, 1,2
-Benzisothiazolin-3-one, n-butyl-p-
Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The emulsion prepared according to the method of the present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports usable for the light-sensitive material are, for example, the above-mentioned RD. No. 17643, page 28, same N
o. 18716, page 647, right column to page 648, left column, and No. 1867. 307105, page 879.

In the light-sensitive material using the emulsion prepared according to the method of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less.
It is more preferably 3 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art.
For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19,
No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1% of the saturated film thickness.
It is defined as the time to reach / 2.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material using the emulsion prepared according to the method of the present invention is provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. It is preferable. In this back layer,
The above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant,
It is preferable to include a coating aid, a surface active agent and the like.
The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material using the emulsion prepared according to the method of the present invention is described in RD. No. 17643
28-29, ibid. 18716, page 651, left column ~
Right column, and No. Development processing can be performed by a usual method described on pages 880 to 881 of 307105.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. As a typical example thereof, for example, 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-β-methoxyethylaniline,
4-Amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-
Hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N-
(3-Hydroxypropyl) aniline, 4-amino-3
-Propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-
N- (4-hydroxybutyl) aniline, 4-amino-
3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N- Ethyl-N- (3-hydroxy-2
-Methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4
-Amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N-
(5-Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N -Bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4
-Hydroxybutyl) aniline and their sulfates,
Hydrochloride or p-toluene sulfonate may be mentioned. Among these, especially 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4- Hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black and white developer,
For example, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol, alone or in combination. Can be used. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but in general, the light-sensitive material 1
Less than 3 liters per square meter, 500m by reducing the bromide ion concentration in the replenisher
It can be 1 or less. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a color developing agent. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Iron (III) is a typical bleaching agent.
An organic complex salt of, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, aminopolycarboxylic acids such as glycol ether diaminetetraacetic acid or citric acid, tartaric acid, Complex salts of malic acid can be used. Among these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-28426, Research Disclosure No. No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A No. 50-140129, a thiazolidine derivative described in JP-A No. 50-140129;
20832, 53-32735, U.S. Pat.
706,561 thiourea derivatives; West German Patent No. 1,127,715; JP 58-16235; iodide salts; West German Patents 966,410, 2,748. , 430, polyamine compounds described in JP-B-45-8836; Others, JP-A-49-40943 and JP-A-49-596.
No. 44, No. 53-94927, No. 54-35727.
Nos. 55-26506 and 58-163940; bromide ions can be used. Above all,
A compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat.
93,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95630 are preferred.
Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleaching and fixing color light-sensitive materials for shooting,
These bleaching accelerators are particularly effective.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, for example, a combination of thiosulfate, thiocyanate, thioether compound and thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294769A.
The sulfinic acid compounds described in US Pat. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

The fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably a pH adjusting agent.
It is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, or JP-A-6-62.
The method of increasing the stirring effect by using the rotating means of No. 2-183461, the photosensitive material is moved while the emulsion surface is brought into contact with the wiper blade provided in the liquid, and the stirring surface is made turbulent to further improve the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Means for improving such stirring are bleaching solution, bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

An automatic processor used for a light-sensitive material using an emulsion prepared according to the method of the present invention is disclosed in JP-A-60-1.
No. 91257, No. 60-191258, No. 60-19
It is preferable to have a photosensitive material conveying means described in No. 1259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, so that it is highly effective in preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material using the emulsion prepared according to the method of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent and forward flow, and various other conditions. Can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is
nal of the Society of Moti
on Picture and Television
Engineers, Vol. 64, p. 248-253
(May 1955 issue). According to the multi-stage countercurrent method described in the document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material. The problem arises. In the processing of color light-sensitive materials, the method of reducing calcium and magnesium ions described in JP-A-62-288838 can be very effectively used as a solution to such a problem. Further, isothiazolone compounds described in JP-A-57-8542, chlorine-based bactericides such as siabendazoles and chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Antibacterial and Antifungal Agents". Chemistry "(1986) Sankyo Publishing, edited by Sanitation Technology" Microbial sterilization, sterilization, and antifungal technology "(1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal" Encyclopedia of Antibacterial and Antifungal Agents "(19
It is also possible to use the fungicide described in 1986).

The pH of the washing water in the processing of the light-sensitive material is
It is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. To be done. Further, the light-sensitive material can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14834 are used.
All known methods described in No. 60-220345 can be used.

In addition, the washing treatment may be followed by further stabilizing treatment. As an example thereof, a dye stabilizing agent and a surfactant used as the final bath of a color light-sensitive material for photographing are contained. A stabilizing bath can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds,
Hexamethylenetetramine or aldehyde sulfite adduct can be mentioned. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material using the emulsion prepared according to the method of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, and No. 3,342,59.
No. 9, Research Disclosure No. 14,85
0 and No. Schiff base type compounds described in Nos. 15 and 159, No. The aldol compound described in 13,924,
Metal salt complexes described in US Pat. No. 3,719,492,
The urethane compounds described in JP-A-53-135628 can be mentioned.

Further, if necessary, various 1-phenyl-3-pyrazolidones may be incorporated for the purpose of promoting color development. Typical compounds are disclosed in JP-A-56-643.
No. 39, No. 57-144547, and No. 58-11.
5438 and the like.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

A silver halide color photographic light-sensitive material using an emulsion prepared according to the method of the present invention is disclosed in JP-B-2-32.
It can also be applied to a film unit with a lens described in, for example, No. 615 and Japanese Utility Model Publication No. 3-39784.

[0187]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 38 g of inert gelatin and 0.7 g of potassium bromide dissolved in 1.1 liter of distilled water were stirred at 70 ° C., and 200 cc of an aqueous solution containing 20 g of silver nitrate, 19 g of potassium bromide and iodine were added thereto. Aqueous solution 28 containing 1 g of potassium iodide
Silver potential (vs SCE) is +70 mV using 0 cc
The silver nitrate solution was added over 6 minutes so that (First-stage addition) After 1 minute, 350 cc of an aqueous solution containing 80 g of silver nitrate, 76 g of potassium bromide and 4 g of potassium iodide in 50.
0 cc, silver potential (vs SCE) is -40 mV
The silver nitrate solution was added over 18 minutes so that (Second-stage addition) Between the first-stage addition and the second-stage addition, 6 × 10 ⁻⁵ mol of thiourea dioxide was added per mol of silver nitrate, and 16 minutes after the start of the second-stage addition. Sodium ethylthiosulfonate is added at 1.5 × 10 ⁻⁵ mol per mol of silver nitrate.

Also, the silver potential (vs SC
Change -40 mV of E) as shown in Table 1 (100)
Emulsions having different surface ratios were prepared.

After desalting, gelatin was added to redisperse the mixture, and the pH was adjusted.
Was adjusted to 6.0 and pAg was adjusted to 8.0. Spectral sensitizing dye E
An amount of xS-4 corresponding to 50% of the saturated coating amount was added at the temperature shown in Table 1. Next, at 60 ° C., sodium thiosulfate, chloroauric acid, the selenium sensitizer of compound-40 and potassium thiocyanate were adjusted to be optimum, and gold / sulfur / selenium sensitization was performed. Table 1 shows the average grain size and grain size distribution (variation coefficient), (100) plane ratio, and sensitizing dye addition temperature of the emulsions Em-A to Em-O thus prepared.

Emulsion Em-P was gold / sulfur sensitized with respect to emulsion Em-O by omitting selenium sensitization in chemical sensitization. Emulsions Em-Q to Em-Y are emulsions Em-
It was prepared by changing the addition amount of the sensitizing dye to F, Em-M and Em-O as shown in Table 1.

Similarly, Table 1 also shows the average grain sizes of the emulsions Em-P to Em-Y, their grain size distribution (variation coefficient), the (100) plane ratio, and the addition temperature of the sensitizing dye. The (100) plane ratio of each emulsion was determined by the Kubelka-Munk method.

[0192]

[Table 1] Next, each layer having the composition shown below was coated on an undercoated triacetyl cellulose support to prepare Sample 101 as a light-sensitive material. (Sample 101) First layer (emulsion layer) Emulsion Em-A As silver 0.60 g / m ² ExC-1 0.70 g / m ² Solv-1 0.04 g / m ² Solv-2 0.04 g / m ² Gelatin 2.5 g / m ² Second layer (protective layer) H-1 0.20 g / m ² B-2 0.10 g / m ² Gelatin 1.00 g / m ² (Samples 102 to 125) Emulsion of Sample 101 Replacing Em-A with emulsions Em-B to Em-Y, and samples 102 to 125
It was created.

These samples 102 to 125 were allowed to stand for 14 hours under the conditions of 40 ° C. and 70% relative humidity and then passed through a yellow filter manufactured by FUJIFILM Corporation and a continuous wedge to 1 /
It was exposed for 40 seconds, the following color development processing was performed, and the density was measured with a red filter.

The logarithm of the exposure amount which gives the cyan density (fog + 0.2) of each of the samples 102 to 125 is 0 for the sample 101.
The relative sensitivity was calculated. Cyan density (fogging +
The gradient of the straight line connecting 0.5) and (fog + 1.8) was determined as the gradation. Further, the maximum color density was determined by giving excessive exposure.

Separately, after leaving these samples 101 to 125 under the conditions of 40 ° C. and 70% relative humidity for 14 hours,
After being placed in an atmosphere having a relative humidity of 55% for 3 hours or more, a load of 10 g was applied with a needle having a diameter of 0.1 mmφ in the same atmosphere, and the emulsion surface was scratched at a speed of 1 cm / sec. After developing this sample under the following conditions, the density was measured with an aperture of 10 μmφ.

The above results are summarized in Table 2.

[0197]

[Table 2] The processing steps are described below.

Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ℃ 33ml 20 liters Bleach 6 minutes 30 seconds 38 ℃ 25ml 40 liters Water wash 2 minutes 10 seconds 24 ℃ 1200ml 20 liters Bleach fixing 4 minutes 20 Second 38 ℃ 25ml 30 liters Water wash (1) 1 minute 05 seconds 24 ℃ (2) to (1) 10 liters countercurrent piping method Water wash (2) 1 minute 00 seconds 24 ℃ 1200ml 10 liters Stabilized 1 minute 05 seconds 38 ℃ 25ml 10 liters Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m length. Next, describe the composition of the treatment liquid. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-3.0 3.2 1,1-diphosphonic acid Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-4.5 5.5 5.5 Hydroxyethylamino] -2-methylaniline sulfate Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleaching solution) Mother liquor (g) Replenishing solution (g) Ferric ethylenediaminetetraacetic acid 100.0 120.0 Sodium trihydrate Ethylenediaminetetraacetic acid di 10.0 10.0 11.0 Sodium salt Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 5.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7 (fixer) mother liquor (g) replenisher (g) ethylenediamine-4 Acetic acid 0.5 0.7 Sodium salt Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Aqueous ammonium thiosulfate solution 170.0 ml 200.0 ml (70%) Add water 1.0 liter 1.0 Liter pH 6.7 6.6 (Stabilizing liquid) Mother liquor (g) Replenishing liquid (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononyl 0.3 0.45 Phenyl ether (average) Degree of Polymerization 10) Ethylenediaminetetraacetic acid di0.05 0.08 Sodium salt water is added to 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8. 0 From the results shown in Table 2, Samples 108, 109, 111, 1 coated with the emulsion prepared according to the method for producing an emulsion of the present invention.
It can be seen that Nos. 12, 114 to 116, and 120 to 122 have high sensitivity, high contrast, high maximum color density, and pressure resistance (increased fogging due to scratching) at a level with no problem.

It is also understood that a higher (100) face ratio is preferable in terms of sensitivity, gradation and maximum color density, and that selenium sensitization is preferable to sulfur sensitization alone.
Further, it is understood that it is preferable to lower the coverage of the spectral sensitizing dye in terms of gradation, maximum color density, and increase in fog due to scratching. Example 2 (Preparation of Sample 201) A back layer as shown below was coated on a triacetyl cellulose support. Further, an undercoat was applied on the side opposite to the back layer, and the emulsion Em-A of Example 1 was used for the third red-sensitive layer to prepare Sample 201, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below. . (Composition of back layer) Methyl methacrylate 1.5 parts-methacrylic acid copolymer (copolymerization mole 1: 1) Cellulose acetate hexahydrophthalate 1.5 parts (hydroxypropyl group 4%, methyl group 15%, acetyl group 8) %, Phthalyl group 36%) Acetone 50 parts Methanol 25 parts Methyl cellosolve 25 parts Colloidal carbon 1.2 parts A coating solution was prepared in the above proportions and applied to white light to a concentration of 1.0. . (Composition of photosensitive layer) The coating amount of each component is the amount of silver expressed in units of g / m ² for silver halide and colloidal silver, and g / m for couplers, additives and gelatin.
Amounts expressed in units of ² and, for sensitizing dyes, are expressed in moles per mole of silver halide in the same layer. (Sample 201) First layer: Antihalation layer Black colloidal silver 0.20 Gelatin 2.30 Second layer: Intermediate layer Cpd-1 0.10 Gelatin 0.80 Third layer: First red sensitive emulsion layer Odor Silver halide emulsion (AgI 3.5 mol%, uniform silver 0.25 AgI type, sphere equivalent diameter 0.06 μm, variation coefficient of sphere equivalent diameter 12%, cubic) ExS-4 1.5 × 10 ⁻³ ExC-1 0.29 ExC-2 0.19 ExC-3 0.05 Solv-1 0.10 Solv-2 0.10 Gelatin 2.40 Fourth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 3. 5 mol%, uniform silver 0.10 AgI type, sphere equivalent diameter 0.10 μm, variation coefficient of sphere equivalent diameter 9%, cubic) ExS-4 6.4 × 10 ⁻⁴ ExC-1 0.12 ExC-20 .04 Solv-1 0.05 Solv-2 0.05 Zera Chin 0.85 Fifth layer: Third red-sensitive emulsion layer Em-A Silver 0.25 ExC-1 0.85 ExC-2 0.55 Solv-1 0.03 Solv-2 0.03 Gelatin 1.10th Six layers: intermediate layer Cpd-1 0.13 gelatin 0.65 Seventh layer: first green emulsion layer Silver iodobromide emulsion (AgI 3.5 mol%, uniform silver 0.42 AgI type, equivalent spherical diameter 0) 0.07 μm, sphere equivalent diameter variation coefficient 11%, cube) ExS-2 1.60 × 10 ⁻³ ExS-3 1.40 × 10 ⁻⁴ ExM-1 0.25 ExM-2 0.10 ExM-30 .05 Solv-1 0.42 gelatin 2.60 Eighth layer: second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 3.5 mol%, uniform silver 0.15 AgI type, sphere equivalent diameter 0.11 μm, Sphere equivalent diameter variation coefficient 9%, cube) ExS-2 9.5 × 10 ^-4 ExS- 3 8.3 × 10 ^-5 ExM-1 0.07 ExM-2 0.03 ExM-3 0.015 ExM-4 0.008 Solv-1 0.15 Gelatin 0.60 9th layer: Third green sensation Emulsion layer Silver iodobromide emulsion (AgI 3.5 mol%, uniform silver 0.21 AgI type, sphere equivalent diameter 0.15 μm, variation coefficient of sphere equivalent diameter 12%, cube) ExS-2 7.8 × 10 ^{− 4} ExS-3 8.8 × 10 ^-5 ExM-1 0.08 ExM-2 0.03 ExM-3 0.02 ExM-4 0.01 Solv-1 0.14 Gelatin 0.90 10th layer: yellow Filter layer Yellow colloidal silver 0.15 Cpd-1 0.10 Cpd-2 0.05 Gelatin 1.0 11th layer: First blue emulsion layer Silver iodobromide emulsion (AgI 2.0 mol%, uniform silver) 0.20 AgI type, sphere equivalent diameter 0.11 μm, sphere equivalent 10% coefficient of variation, ^{cubic) ExS-1 1.8 × 10 -3} ExC-1 0.03 ExY-1 0.35 ExY-2 0.35 Solv-1 0.25 Gelatin 1.10 12th layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2.0 mol%, uniform silver 0.22 AgI type, sphere equivalent diameter 0.15 μm, variation coefficient of sphere equivalent diameter 12%, cubic) ExS-1 1. 3 × 10 ⁻³ ExC-1 0.01 ExY-1 0.26 ExY-3 0.05 Solv-1 0.09 Gelatin 0.45 13th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2.0 mol%, uniform silver 0.37 AgI type, sphere equivalent diameter 0.20 μm, variation coefficient of sphere equivalent diameter 13%, cubic) ExS-1 1.0 × 10 ⁻³ ExC-1 0.003 ExY− 1 0.07 Solv-1 0.02 Gelatin 0.60 14th layer : 1st protective layer UV-1 0.05 UV-2 0.24 Solv-2 0.12 gelatin 0.50 15th layer: 2nd protective layer B-1 (diameter 1.70 micrometer) 0.01 B-2 (Diameter 1.70 μm) 0.01 B-3 0.09 H-1 0.30 In addition to the above, 1,2-benzisothiazolin-3-one (200 pp on average for gelatin was added to this sample 201.
m), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added.

Further, B-4, B-5, W-1, W-2, F
It is also added to -1 to F-8 and F-9 to F-12.

The structural formulas of the compounds used to prepare each sample in the above Examples 1 and 2 are shown in Chemical Formulas 11 to 22 below.

[0202]

[Chemical 11]

[0203]

[Chemical 12]

[0204]

[Chemical 13]

[0205]

[Chemical 14]

[0206]

[Chemical 15]

[0207]

[Chemical 16]

[0208]

[Chemical 17]

[0209]

[Chemical 18]

[0210]

[Chemical 19]

[0211]

[Chemical 20]

[0212]

[Chemical 21]

[0213]

[Chemical formula 22] (Preparation of Samples 202 to 225) Samples 202 to 225 were prepared by replacing the emulsion Em-A in the fifth layer of Sample 201 with the emulsions Em-B to Em-Y.

Samples 201 to 225 were measured at 40 ° C. and a relative humidity of 70.
% For 14 hours, then exposed to white light through a continuous wedge for 1/40 seconds, and subjected to the following color development treatment to measure the density.

The logarithm of the exposure giving the cyan density (fog + 0.1) of each sample was determined by relative sensitivity with sample 101 being 0, and the cyan density (fog + 0.1) and (fog + fog +
The gradient of the straight line connecting 0.6) was determined as the gradient. Excessive exposure was given and the maximum emission density was also determined.

Separately, samples 101 to 125 were tested for pressure resistance in the same manner as in Example 1 except that a load of 20 g was applied with a needle having a diameter of 0.1 mm.

From the above results, it was confirmed that the object of the present invention can be achieved also in the multilayer color light-sensitive material as in Example 1 as in Example 1. Development processing method of multilayer color light-sensitive material Processing step Temperature (° C) Time 1. Pre-bath 27 ± 1 10 seconds 2. Backing removal 27-385 seconds and spray water washing 3. Color development 41.1 ± 0.1 3 minutes 4. Stop 27-38 30 seconds 5. Bleach acceleration 27 ± 1 30 seconds 6. Bleach 38 ± 1 3 minutes 7. Washing with water 27-38 1 minute 8. Stationary 38 ± 12 2 minutes 9. Washing with water 27-38 2 minutes 10. Stability 27-38 10 seconds Prescription of each treatment liquid (1) Pre-bath Prescription value Water at 27-28 ° C 800 ml Borax (10-hydrate) 20.0 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1.0 g Water In addition, 1.00 liter pH (27 ° C.) 9.25 (3) Color development Water having a prescribed value of 21 to 38 ° C. 850 ml Kodak Anticalcium No. 4 (registered trademark) 2.0 ml Sodium sulfite (anhydrous) 2.0 g Eastman Antifog No. 9 (registered trademark) 0.22 g sodium bromide (anhydrous) 1.20 g sodium carbonate (anhydrous) 25.6 g sodium bicarbonate 2.7 g color developing agent; 4.0 g 4-amino-3-methyl-N-ethyl -N-([beta] -methanesulfonamidoethyl) -aniline Water was added to 1.00 liter pH (27 [deg.] C) 10.20 (4) Stop Water with a prescribed value of 21-38 [deg.] C 900 ml 7.0N sulfuric acid 50 ml Water was added 1.00 liter pH (27 ° C) 0.9 (5) Bleach accelerating liquid Prescription value Water 900 ml Sodium metabisulfite (anhydrous) 10.0 g Glacial acetic acid 25.0 ml Sodium acetate 10.0 g EDTA-4Na 0.7 g PBA 5.5 g Water was added 1.00 liter pH (27 ° C.) 3.8 ± 0.2 PBA was 2-dimethylaminoethylisothieurea dihydrochloride Represents (6) Bleaching solution Prescription value Water at 24-38 ° C 800 ml Gelatin 0.5 g Sodium persulfate 33.0 g Sodium chloride 15.0 g Sodium monophosphate (anhydrous) 9.0 g Phosphoric acid (85%) 2.5 ml Water 1.00 liter pH (27 ° C) 2.3 ± 0.2 (8) Fixing Prescription value Water at 20 to 38 ° C 700 ml Kodak Anticalcium No. 4 (registered trademark) 2.0 ml 58% antimonium thiosulfate solution 185 ml sodium sulfite (anhydrous) 10.0 g sodium bisulfite (anhydrous) 8.4 g Water is added to 1.00 liter pH (27 ° C.) 6.5 (10) Stable water with a prescribed value of 21 to 27 ° C. 1.00 liter Kodak Stabilizer 0.14 ml Additive (registered trademark) Formalin (37.5% solution) 1.50 ml (wash water) Normal tap water

Claims (5)

[Claims] 1. A method for producing a silver halide emulsion, which comprises chemical ripening in the presence of a spectral sensitizing dye after grain formation of a silver halide emulsion, wherein the silver halide emulsion has an average (100%) of all grains. ) An emulsion comprising regular crystal silver halide grains having an area ratio of 60% or more, wherein the spectral sensitizing dye is added at a temperature of 25 ° C. or more and 50 ° C. or less. Method. 2. The method for producing a silver halide emulsion according to claim 1, wherein the amount of the spectral sensitizing dye added is 2% or more and 25% or less of the saturated coverage of the silver halide emulsion. 3. The method for producing a silver halide emulsion according to claim 1, wherein the normal silver halide grains have an average silver iodide content of 0.1 mol% or more and 7 mol% or less. 4. The method for producing a silver halide emulsion according to claim 1, wherein the normal crystal silver halide grains are sensitized with selenium. 5. The method for producing a silver halide emulsion according to claim 1, wherein the spectral sensitizing dye is a cyanine dye.