JPH08194277A - Manufacture of silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance stability in manufacture and, especially, to reduce deterioration of performance during storage, and to enhance resistance to stagnation of a coating fluid and aging stability under high temperature and high humidity by adding a specified step for specifying a silver potential at the time of preparing the emulsion and a specified radical scavenger. CONSTITUTION: The step of regulating the silver potential to the range of -200 to -50mV is included into the process of preparing the emulsion and the radical scavenger to be incorporated is represented by formula I or II in which each of R and R' is, independently, an alkyl or aryl group, and each of R1 and R2 is, independently, a hydroxyamino or hydroxy group or the like. The radical scavenger is designated as the compound capable of substantially decoloring carbionxyl (reducing light absorbance at 230nm, when a 0.05mmol/dm<3> ethanol solution of the carbinoxyl are mixed with 2.5mmol/dm<3> ethanol solution of the compond to be tested at <=25 deg.C by the stopped-flow method and change of the absorbance at 430nm with the lapse of time is measured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material. More specifically, it is excellent in production stability, particularly in performance deterioration during storage of an emulsion, excellent in stagnation of coating solution, and high temperature and high humidity conditions. The present invention relates to a method for producing a silver halide emulsion having excellent stability under the following conditions and a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is manufactured by a process such as grain formation, desalting, chemical sensitization, etc., and an additive, a coupler dispersion and an additive are added to a prepared silver halide emulsion as needed. These are mixed, coated on a support, dried, and then cut into a required size and packaged.

The above-mentioned steps of silver halide emulsion production are usually batch-prepared in a reaction vessel whose temperature is controlled to a required temperature. In the reaction vessel, the silver halide grains are present as a suspension using gelatin as a binder, and the liquid surface thereof is in contact with air. During grain formation and chemical sensitization,
It is often stirred at a high temperature, and when desalting, the particles often take a long time to settle at a relatively low temperature. The silver halide emulsion is thus prepared under conditions susceptible to dissolved oxygen.

Performing the emulsion preparation under deoxidation is ideal in terms of removing the influence of oxygen, but it is difficult to realize it in view of the restrictions in the actual production equipment. The prevention of deterioration of photographic performance during the preparation of emulsions has been studied so far. For example, US Pat. No. 5,079,138.
The publication discloses the use of thiosulfonic acid in order to prevent photographic performance deterioration due to silver nuclei formed unintentionally at the time of emulsion preparation, but the effect is insufficient, and the adverse effect of dissolved oxygen is adversely affected. Is not completely prevented.

Next, the silver halide emulsion thus prepared may be immediately coated on a support, or if necessary, the prepared silver halide photographic emulsion is once in a sol or gel state. You may apply after storing for a while. It is generally stored for a certain period of time after preparation due to restrictions such as a manufacturing apparatus and a manufacturing method.

However, during storage of the silver halide emulsion,
Photographic performance (for example, sensitivity and fog) is likely to change, and it is preferable to make this change during storage as small as possible. Therefore, the silver halide emulsion after preparation is generally stored at a low temperature of, for example, about 5 ° C. so as to suppress the change with time as much as possible.

Researches for suppressing the change with time have been made so far. For example, Research Disclosure Nos. 10152 and 13941 disclose a method of storing a silver halide emulsion in a freeze-dried state. . However, this method has the drawbacks that the production facilities are largely restricted and that in the case of the high-sensitivity emulsion, fog increases at the moment of freeze-drying.

Further, British Patent No. 1,159,385 and Japanese Patent Application Laid-Open No. 1-287672 disclose a method for improving storage stability by storing in a degassed state with oxygen, such as nitrogen substitution. These methods certainly work,
Although it was a useful invention, it seems that there are also major restrictions on manufacturing equipment, and it is probably difficult to completely block oxygen, but the effect is often insufficient. , Further improvement was desired.

[0009] Japanese Patent Laid-Open Nos. 01-319030 and 04
-314049, JP-A-04-317051, JP-A-04-365032, JP-A-05-45772,
Japanese Patent Laid-Open Nos. 05-72666 and 05-119427
JP-A No. 2000-242242 discloses various compounds having a —NHOH group, and an improvement effect has been obtained by adding these compounds at the time of coating a light-sensitive material, but there is no example of addition to the emulsion itself. As a matter of course, no effect was obtained on the temporal stability of the emulsion itself. In addition, improvement of stagnation property of coating liquid is also desired. In the production, coating is started after emulsions, emulsions and various chemicals are mixed and dissolved. The change in performance over time after mixing and dissolution is called the stagnation property of the coating liquid. Due to increase in production scale and troubles during coating,
In a dissolved state, it may be necessary to aging for several hours, and the performance stability over time is an important performance for stabilizing manufacturing. JP-A-63-298240 discloses that in order to improve the stagnation property of the coating liquid and the performance variation with time,
Although a method of containing a trimethine cyanine dye and a monomethine dye has been disclosed, further improvement techniques such as further increase of stagnation time due to expansion of production scale and increase of coating failure due to high-speed coating are desired.

Further, in JP-A-6-186657, a core consisting essentially of silver iodobromide and silver iodobromide having a silver iodide content lower than the silver iodobromide content of the core or substantially consisting thereof are disclosed. It contains silver iodobromide grains composed of a shell made of silver bromide, and the relative standard deviation of the silver iodide content of each grain is 2
During the process from chemical ripening to coating, a substantially water-insoluble spectral sensitizing dye was added to a silver halide emulsion of 0% or less in a solid state without using an organic solvent, and fine grain iodine was added. It is disclosed that the stagnation property of the coating solution is improved by producing a silver halide emulsion by adding silver halide. However, this method imposes restrictions on the grain structure even when silver halide grains are formed, and also greatly restricts during chemical sensitization, making it difficult to widely apply it to general emulsions.

[0011]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned problems, to improve production stability, particularly less deterioration of performance during storage, excellent coating liquid stagnation property, and high temperature and high humidity. The object of the present invention is to provide a method for producing a silver halide emulsion excellent in stability over time under the conditions and a silver halide photographic light-sensitive material containing the same.

[0012]

The object of the present invention has been achieved by the manufacturing method and the silver halide photographic light-sensitive material described in claims 1 to 3.

(1) -200 mV or more during emulsion preparation-5
A method for producing a silver halide emulsion comprising a step of silver potential of 0 mV or less and containing a radical scavenger represented by the general formula [A] or [B].

[0014]

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In the general formula [A], R and R'may be the same or different and each represents an alkyl group or an aryl group. In the general formula [B], R ₁ and R ₂ may be the same or different and each is a hydroxyamino group, a hydroxyl group, an amino group, an alkoxylamino group, an arylamino group, an alkoxy group, an arylocio group, an alkylthio group. Represents an arylthio group, an alkyl group or an aryl group.

(2) -200 mV or more at the time of emulsion preparation -5
A method for producing a silver halide emulsion comprising a step of silver potential of 0 mV or less and containing a radical scavenger represented by the general formula [C].

[0017]

[Chemical 4]

In the general formula [C], R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom, an alkyl group,
Alkenyl group, aryl group, heterocyclic group, alkyloxy arbonyl group, aryloxycarbonyl group, acyl group, sulfonyl group, carboxyl group, carbamoyl group,
It represents a sulfamoyl group, a halogen atom or -X-R _a0 . Here, -X- is -O-, -S- or -N.
Represents (R _a6 ) −. R _a0 is an alkyl group, an alkenyl group,
It represents an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _a6 represents a hydrogen atom or a group defined by R _a0 . Of the groups R _{a1 to} R _a5 , the substituents in the ortho positions may be bonded to each other to form a 5- to 7-membered ring. However,
Each group of R _{a1 to} R _a5 is not a hydrogen atom at the same time,
When R _a3 is a halogen atom, —O—R _a0 or —S—R _a0 , at least one of R _{a1 and} R _a5 is an alkyl group.

(3) A silver halide photographic light-sensitive material containing an emulsion according to the emulsion manufacturing method of claim 1 or 2, wherein the radical scavenger is added after desalting and dispersing.

The light-sensitive material of the present invention will be described in more detail below.

As a factor of the performance deterioration occurring during the preparation of the silver halide emulsion, the change of the emulsion grains due to the dissolved oxygen is considered. Typical examples of performance deterioration include a decrease in sensitivity and an increase in fog, a change in sensitivity gradually decreasing during storage, and a change in fog gradually increasing.

By carrying out the grain formation in an atmosphere in which the dissolved oxygen in the suspension used during grain formation or the aqueous solution added is removed by substituting it with argon, the above-mentioned deterioration in photographic performance is reduced. This indicates not only that dissolved oxygen is a factor of deterioration of photographic performance, but also that the effect of removing dissolved oxygen is great. However, this method is likely to be due to large restrictions on manufacturing equipment, and probably because it is difficult to completely shut off oxygen, but in many cases the effect is insufficient. Was desired.

Further, in order to suppress changes during storage as much as possible,
The aforementioned British Patent No. 1,159,385, Japanese Patent Laid-Open No. 1-25.
I tried a method of improving storage stability by storing in an oxygen-deaerated state, such as by nitrogen substitution described in No. 87,672, but it was certainly effective, but there were large restrictions on manufacturing equipment, As described above, it has drawbacks such as insufficient effect. However, from these experimental examples, it was suggested that oxygen existing during storage influences the deterioration of the silver halide photographic emulsion during storage.

Therefore, as a result of diligent studies, the present inventors have prepared a silver halide emulsion in the presence of a radical scavenger as a result of diligent studies to substantially block the influence of oxygen during the preparation and storage of the silver halide emulsion. As a result, the inventors have found that the deterioration of the photographic performance as described above can be remarkably improved, and have reached the present invention.

It is known that a silver halide photographic light-sensitive material contains a radical scavenger according to the present invention as defined below.

Japanese Examined Patent Publication Nos. 43-4133 and 49-106
92, JP-A-57-176032, 56-527.
34, 58-28714, 61-91651.
No. 59-971134 and 59-162546.
No., UK Patent No. 2,054,187, US Patent No. 3,
582,333, 3,671,248, 3,9
No. 02,905 and No. 3,522,053, the development of a light-sensitive material (not a silver halide photographic emulsion) is improved, fog is prevented, gradation is improved, raw storage stability is improved, and latent image is latent image. It is known to contain various compounds within the scope of the radical scavenger defined in the present invention for the purpose of improving storage stability.

However, these inventions are clearly intended to improve the performance of the silver halide photographic light-sensitive material itself, and in the examples, they are contained by mixing with a silver halide photographic emulsion immediately before coating, or at an intermediate level. It does not specify the addition to layers or the timing of addition.

Therefore, the radical scavenger is used for the purpose of preventing the performance deterioration of the preparation and storage stability of the silver halide photographic emulsion, stabilizing the stagnation of the coating solution, and improving the stability over time under high temperature and high humidity conditions. , Especially the general formula [A],
It is a completely novel invention that the compounds represented by [B] and [C] are remarkably effective in the preparation of an emulsion including a step of low silver potential.

Although the mechanism of the present invention is not always clear, at the present time, it has a radical scavenging ability to substantially prevent the influence of oxygen or radical species derived from oxygen on silver halide, and at the same time, direct halogen A compound that does not affect silver halide and exerts no adverse effect is considered most preferable. In this sense, the general formula [A] containing certain hydroxylamines, phenols, tocopherols, etc.
The compound represented by [B] or [C] is most preferable.

Next, the radical scavenger used in the present invention will be described. The radical scavenger in the present invention refers to galvinoxyl of 0.
05 mmol / dm ³ ethanol solution and 2.5 of test compound
It refers to a compound which is mixed with a mmol / dm ³ ethanol solution by the stopped-flow method and the time change of the absorbance at 430 nm is measured to substantially decolorize galvinoxyl (decrease the absorbance at 430 nm). The decolorization rate constant of galvinoxyl determined by the above method is preferably 0.01 dm ³ / mmol · s or more, more preferably 0.1 dm ³ / mmol · s or more. The method for determining the radical scavenging rate using galvinoxyl is
Microchemical Journal 31, 18-21 (1985)
For the stopped-flow method, for example, spectroscopic studies
Vol. 19, No. 6, (1970), p. 321.

In the present invention, it is more preferable to use a compound represented by the general formula [A], [B] or [C] as the radical scavenger.

First, the compound represented by the following general formula [A] or [B] will be described in detail.

[0033]

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In the general formula [A], R and R'may be the same or different and each is an alkyl group (for example, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, hexyl, cyclohexyl, t-octyl, Decyl, dodecyl, hexadecyl, benzyl) or aryl groups (eg phenyl, naphthyl).

In the general formula [B], R ₁ and R ₂ may be the same or different and each represents a hydroxylamino group, a hydroxyl group, an amino group or an alkylamino group (for example, methylamino, ethylamino, diethylamino, methylethyl). Amino, propylamino, dibutylamino,
Cyclohexylamino, t-octylamino, dodecylamino, hexadecylamino, benzylamino, benzylbutylamino), arylamino groups (eg phenylamino, phenylmethylamino, diphenylamino, naphthylamino), alkoxy groups (eg methoxy, ethoxy, Butoxy, t-butoxy, cyclohexyloxy,
Benzyloxy, octyloxy, tridecyloxy,
Hexadecyloxy), aryloxy groups (eg phenoxy, naphthoxy), alkylthio groups (eg methylthio, ethylthio, i-propylthio, butylthio, cyclohexylthio, benzylthio, t-octylthio,
Dodecylthio), arylthio groups (eg phenylthio, naphthylthio), alkyl groups (eg methyl, ethyl, propyl, butyl, cyclohexyl, i-amyl,
sec-hexyl, t-octyl, dodecyl, hexadecyl) and aryl groups (eg phenyl, naphthyl).

The groups represented by R, R ', R ₁ and R ₂ represented by the general formula [A] or [B] may be further substituted with a substituent. Examples of these substituents include an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group and an arylamino group. ,
Examples thereof include a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and an acyloxy group. In the general formula [A], it is preferred that R and R'are alkyl groups. On the other hand, in the general formula [B], R ₁
And R ₂ is a hydroxyamino group, an alkylamino group,
A group selected from alkoxy groups is preferred. Particularly preferred compounds of the present invention can be represented by the general formula [B '].

[0037]

[Chemical 6]

[0038] In the formula, R ₂ represents a same group as R ₂ in the general formula (B), the same as in the preferred group of the general formula (B). Specific examples of the compounds represented by formulas [A] and [B] of the present invention are shown below, but the present invention is not limited thereto.

[0039]

[Chemical 7]

[0040]

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[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

These compounds of the present invention are described in J.Org. Chem.,
27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('51),
It can be easily synthesized by the method described in JP-B-49-10692 or the like.

Next, the compound represented by the general formula [C] will be described in detail.

[0048]

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The substituent described in the present invention may further have a substituent.

In the general formula [C], R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom or an alkyl group (for example, methyl, t-butyl, t-octyl, cyclohexyl, 2'-hydroxybenzyl, 4 '). -Hydroxybenzyl, carboxyethyl, preferred carbon absorption is 1
To 30), an alkenyl group (for example, allyl or vinyl, preferably 2 to 30 carbon atoms), an aryl group (for example, phenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, preferably phenyl having 6 to 30 carbon atoms and substituted). Phenyl), heterocyclic groups (eg 4-morpholinyl,
1-piperidyl and 1-pyrrolidinyl, preferably a saturated heterocycle having 4 to 15 carbon atoms), an alkyloxycarbonyl group (eg, ethoxycarbonyl, hexadecyloxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl, 2,4) -Di-t-butylphenoxycarbonyl), an acyl group (eg acetyl, benzoyl, myristoyl), a sulfonyl group (preferably an alkylsulfonyl group such as methanesulfonyl, an arylsulfonyl group such as benzenesulfonyl, 2-hydroxybenzenesulfonyl), a carboxyl group. Groups, carbamoyl groups (eg dimethylcarbamoyl, methylphenylcarbamoyl, dodecylcarbamoyl), sulfamoyl groups (eg dimethylsulfamoyl, dodecylsulfamoyl), ha Gen atom (e.g., chlorine, bromine, fluorine) represent or -X-R _a0.

--X-- is --O--, --S-- or --N (R
_a6 ) _-represents . R _a0 is an alkyl group (eg, methyl, isopropyl, octyl, benzyl, hexadecyl, methoxyethyl, cyclohexyl, and the preferred carbon absorption is 1
To 26), an alkenyl group (eg, allyl or vinyl, preferably having 2 to 26 carbon atoms), an aryl group (eg, phenyl, 4-methoxyphenyl, naphthyl, preferably phenyl having 6 to 30 carbon atoms or substituted phenyl). , A heterocyclic group (eg, 2-tetrahydropyranyl,
Pyridyl), acyl groups (eg acetyl, benzoyl,
Tetradecanoyl) or a sulfonyl group (preferably an alkylsulfonyl group such as methanesulfonyl, octanesulfonyl, an arylsulfonyl group such as benzenesulfonyl), and R _a6 represents a hydrogen atom or a group defined by R _a0 . Of the groups R _{a1 to} R _a5 , substituents in the ortho positions may be bonded to each other to form a 5- to 7-membered ring (eg, chroman ring, indane ring), which forms a spiro ring or a bicyclo ring. You can do it.

However, if each group of R _{a1 to} R _a5 is not a hydrogen atom at the same time and R _a3 is a halogen atom, —O—R _a0 or —S—R _a0 , then R _a1 and R _a5 At least one is an alkyl group.

Among the compounds represented by the general formula [C], preferred compounds from the viewpoint of the effects of the present invention are listed.

A compound having a substituent at any position of R _a1 , R _a3 or R _a5 and having a hydrogen atom at the α-position of at least one of the substituents.

A compound in which R _a1 is substituted with an alkyl group.

Compounds in which R _a1 is substituted with an acylamino group.

A compound in which the substituents in the ortho positions among the groups R _{a1 to} R _a5 are bonded to each other to form a chroman ring, a Claman ring or an indane ring.

Among the compounds represented by the general formula [C], the particularly preferred compounds from the viewpoint of the effect of the present invention are the general formulas (CI) and (C-II) shown below, and the most preferred compounds are the general formulas. (C-II).

[0059]

[Chemical 15]

In the general formula (CI), R _a10 represents an alkyl group, R _a11 represents an alkyl group, an alkoxy group,
Alternatively, it represents an aryloxy group. R _a2 , R _a4 and R
_a5 represents a group defined by the general formula [C]. General formula (C
In -I), a compound in which R _a2 , R _a4 and R _a5 are a hydrogen atom, an alkyl group or an alkoxy group is preferable from the viewpoint of the effect of the present invention.

In the general formula (C-I), R _a2 and R _a11 , R _a2 and R _a10 or R _a4 and R _a11 are connectors,
A compound forming a signet ring, a coumaran ring, a chroman ring or their spiro ring or bicyclo ring is also preferable.

In the general formula (C-II), R _a1 2 to R a
_a15 represents an alkyl group, and R _a15 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group or a sulfonyl group. X _a1 represents a single bond, —O—, —S— or —CH (R _a17 ) —. Here, R _a17 represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (C-II), in view of the effect of the present invention, a compound in which R _a16 is a hydrogen atom, or X _a1 is —CH (R _a17 ).
The compound represented by the formula (-) is preferable, and in this case, when R _a17 is a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 11), it is particularly preferable.

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

[0064]

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[0065]

[Chemical 17]

[0066]

Embedded image

[0067]

[Chemical 19]

[0068]

Embedded image

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

[0072]

[Chemical formula 24]

[0073]

[Chemical 25]

[0074]

[Chemical formula 26]

[0075]

[Chemical 27]

[0076]

[Chemical 28]

[0077]

[Chemical 29]

Other preferred compound examples and synthetic methods of the compound represented by the general formula [C] of the present invention are described in US Pat. Nos. 3,432,300, 3,573,050 and 3,574. , 627, 3,700, 455,
No. 3,764,337, No. 3,930,866
No. 4,113,495, No. 4,120,72
No. 3, No. 4,268,593, No. 4,430,4
25, 4,745,050, U.S. Pat. No. 2,0
No. 43,931, European Patent No. 176,845, Japanese Patent Publication Nos. 48-31256, 54-12055, and Japanese Patent Laid-Open Publication No.
No. 137258, No. 1-137254 and the like.

Table 1 shows the decolorization rate constants of galvinoxyl, some of the radical scavengers.

[0080]

[Table 1]

In the method of the present invention, the radical scavenger compound may be added after being dissolved in water, alcohol, ester or ketone or a mixed solvent thereof. In the case of being dissolved in water, if the solubility is increased by increasing or decreasing the pH, the compound may be dissolved by increasing or decreasing the pH and then added. Soluble radical scavengers may also be added in dispersed form in aqueous gelatin solution.

In the method of the present invention, the addition amount of the radical scavenger compound is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide to be added,
The amount is more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol, and further preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol.

In the method of the present invention, the radical scavenger may be added at any of the grain forming step (including physical ripening), the demineralized water washing step, and the chemical sensitization step, but it is added after the desalted water washing step. Is more preferable.

The silver halide grains used in the present invention will be described below.

The silver halide grains used in the present invention are
It is characterized by including a step of silver potential of -200 mV or more and -50 mV or less at the time of emulsion preparation. Preferably -1
70 mV or more and -50 mV or less, more preferably -150
It is necessary to include a step of silver potential of mV or more and -50 mV or less. The amount of silver placed in the silver potential atmosphere is preferably 10% or more, more preferably 20%, based on the total amount of silver.
Or more, More preferably, it is 30% or more. When the amount of silver placed in a low silver potential atmosphere is less than 10%, there is a high possibility that adverse effects such as increased fog will occur.

The value of the silver potential in the present invention is expressed by a saturated calomel electrode (SCE).

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as Rhodan silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When it is desired to accelerate the development / desilvering (bleaching, fixing and bleach-fixing) steps, silver halide grains having a high silver chloride content are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide.
A preferable silver iodide content is 0.1 in the case of a photographic light-sensitive material represented by color negative and color reversal.
To 30 mol% of silver iodide, more preferably 0.2 to 20 mol%, and particularly preferably 0.1.
It is 3 to 15 mol%. It is preferable that the silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains. The typical one is Japanese Patent Publication No. 43-131.
62, JP-A-61-215540, and JP-A-60-2.
No. 22845, JP-A-60-143331, JP-A-6-63
It is a core-shell type or double structure type grain having a halogen composition in which the inside and the surface layer of the grain are different as disclosed in, for example, 1-75337. 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 particles, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are JP-A-59
-133540, JP-A-58-108526, European Patent 199,290A2, and JP-B-58-24772.
And 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 a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan and silver carbonate can be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as lead oxide may be used as long as a joint structure is possible.

In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core portion and a high shell portion are preferable.
Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of the particles having these structures may be a clear boundary or an unclear boundary. In addition, a positive embodiment in which the composition is positively and continuously changed is also a preferred embodiment. In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have 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. Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. Inverse correlation depending on the purpose,
Correlations with other halogen compositions can be chosen. For this purpose, it is preferable to mix two or more emulsions having different compositions.

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.

The silver halide grains used in the present invention, even if they are normal crystals not containing twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photograph (Corona Publishing Co.), p. 163, eg, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary.
In the case of normal crystal, a cube consisting of (100) plane, (11
An octahedron composed of 1) planes is disclosed in JP-B-55-42737 and JP-A-60-222842 (110).
A dodecahedral grain composed of planes can be used. Further, Journal of Imaging Science, Vol. 30, p. 247, (hll) plane particles typified by (211) as reported in 1986, and typified by (331) (h
hl) plane particles, (hk0) plane particles typified by the (210) plane and (hkl) plane particles typified by the (321) plane also require devising in the preparation method, but can be selected and used according to the purpose. . A tetrahedral particle in which the (100) plane and the (111) plane coexist in one particle, a particle in which the (100) plane and the (110) plane coexist, or a particle in which the (111) plane and the (110) plane coexist. Particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. The use of tabular grains having aspect ratios greater than 1 is especially preferred in the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleve (Cleve, Photography Theory and Pra
ctice (1930), p. 131; Gatov, Photographic Science and Engineering (Gut
off, Photographic Science and Engineering), 14th
Vol. 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by the sensitizing dye, and the above-cited US Pat.
No. 226. The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and less than 100. More preferably 2 or more and less than 20,
It is particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like.
A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form. As the grain size of tabular grains, a circle-equivalent diameter of the projected area is often used, but US Pat. No. 4,748,106
Particles having an average diameter of 0.6 μm or less, as described in No. 3, are preferable for improving image quality. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less in order to improve the sharpness.

In order to improve the sharpness, it is important to select the grain thickness in consideration of the wavelength of the light incident on or exposed to the photosensitive material. 0.0 for a layer that scatters blue light of 400 to 500 nm or a layer that is sensitive to blue light
It is preferred to place particles 8 to 0.10 microns thick. Next preferred is a thickness of 0.19 to 0.21 micron. 0.11 to 0.13 for layers that scatter green light of 500 to 600 nm or layers that are sensitive to green light
It is preferred to deposit particles that are micron thick, and next preferred is a thickness of 0.23 to 0.25 micron. Particles with a thickness of 0.14 to 0.17 micron are preferably arranged in the layer which scatters red light of 600 to 700 nm or is sensitive to red light, and the second preferred is 0.28 to 0.30. It is micron thick. Particles having a thickness of 0.17 to 0.19 μm are preferably arranged in the layer that scatters infrared light or the layer that is sensitive to infrared light. When one photosensitive layer is composed of a plurality of photosensitive layers having different sensitivities, it is best to dispose particles having a preferable thickness in all layers, and the second preferable is to dispose in a photosensitive layer further away from the support. Is. It is particularly preferable to use a combination of particles having a preferable thickness in each photosensitive layer, for example, to arrange particles having a preferable thickness in both the blue light sensitive layer and the green light sensitive layer. Any combination of blue light, green light, and red light sensitive layers can be selected. Further, JP-A-63-
The grains described in No. 163451, which define the grain thickness and the interplanar distance between twin planes, are also preferable.

Further, more preferable results may be obtained by using monodisperse tabular grains having a narrow grain size distribution. U.S. Pat. No. 4,797,354 and JP-A-2
No. 838 describes a method for producing monodisperse hexagonal tabular grains having a high tabularization rate. Also, European Patent No. 514,
No. 742 describes a method of producing tabular grains having a variation coefficient of grain size distribution of less than 10% using a polyalkylene oxide block copolymer. It is preferable to use these tabular grains in the present invention. Further, particles having a high coefficient of variation in particle thickness of 30% or less and high thickness uniformity are also preferable. The amount of these polymers to be used is 0. 0 with respect to the amount of Ag in the AgNO ₃ aqueous solution added at the time of nucleation.
The amount is preferably 1 to 50% by weight, more preferably 0.2 to 20% by weight.

In the present invention, it is preferable to use a monodisperse emulsion.

As for the silver halide grains in the monodisperse emulsion, the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% of the total weight of silver halide grains.
It is preferably not less than 70%, more preferably not less than 70%, further preferably not less than 80%.

[0098] The average particle diameter r Here, the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri means the particle size at which a maximum. (Three significant figures and the least significant figure are rounded off)

The term "particle size" used herein means the diameter of spherical silver halide grains, and the particle size of a cubic or non-spherical grain when the projected image is converted into a circular image of the same area. Indicates the diameter.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times, and measuring the particle diameter on the print or the area at the time of projection. (The number of measured grains is indiscriminately 1000 or more.) In the present invention, a highly monodisperse emulsion is preferable, and a variation coefficient (monodispersity) defined by the following formula is preferably 20 or less. , And more preferably 1
It is 5 or less.

(Monodispersity) Coefficient of variation (σ / r) = (particle size standard deviation / average particle size) × 1
Here, the average particle size and the particle size standard deviation are obtained from ri defined above. Monodisperse emulsion is disclosed in JP-A-54-48521.
No. 58-49938, No. 60-122935 and the like.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select dislocations or curved dislocations that are linearly introduced with respect to a specific direction of the crystal orientation of the particles, or they can be introduced throughout the particles or only at specific sites of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1 or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in US Pat. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. JP-A-58-106532, JP-A-60-221
Examples are the part of the crystals described in U.S. Pat. No. 320, for example the method of drilling holes in the centers of vertices or planes, or the ruffled particles described in U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. Preferably, grains having a size of 0.1 micron or more and 3 microns or less are used as the photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. 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 using a monodisperse emulsion, the coefficient of variation is 25% or less,
It is preferable to use an emulsion having a size distribution of 20% or less, and more 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, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montell (P. G.
lafkides, Chimie et Physique Photographique Paul Mo
Ntel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion).
Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (V.
L. Zelikman et al, Making and Coating Photographic
It can be prepared by the method described in Emulsion, Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. 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 the addition method can be selected from total addition at once, divided addition in plural times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, European Patents 273,429, 273.
No. 430 and West German Laid-Open Patent No. 3,819,241 and the like, which 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,
The particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. 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 US Pat. Nos. 2,996,287, 3,342,605, 3,415,650 and 3,785,777. , West German Published Patents 2,556,885, 2,555,364
It can be used by selecting from the methods described in No.

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. All of these ripening agents can be added to the dispersion medium in the reactor before adding the silver and halide salts,
It is also possible to add halide salts, silver salts or peptizers and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages. Ammonia, thiocyanate (Rhodan potassium, Rhodan ammonium, etc.), organic thioether compound (for example, US Pat. Nos. 3,574,628, 3,021,215, 3,057,724 and 3,038, No. 805, No. 4,276,374, No. 4,297,439, No. 3,704,130, No. 4,782,013, JP-A No. 57-104926, etc.), Thione compounds (for example, JP-A-5
3-82408, 55-77737, U.S. Pat. No. 4,221,863 and the like, tetra-substituted thioureas, compounds described in JP-A-53-144319), and JP-A- No. 57-202531, which can promote the growth of silver halide grains, mercapto compounds and amine compounds (for example, JP-A-54-10071).
No. 7, etc.) and the like.

Gelatin is advantageously used as the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As gelatin, lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan.No. P3
0 (1966), an enzyme-treated gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 ° 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,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. 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.

During preparation of the emulsion of the present invention, 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, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. 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. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3) 2,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ],
(NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (N
Etc. _{H 4) 3 RhCl 6, K} 4 Ru (CN) 6 and the like. As a ligand of a coordination compound, halo, aco, cyano,
It can be selected from cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. Although these may use only one type of metal compound, 2
One kind or a combination of three or more kinds may be used.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
l, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) 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. It is also possible to add it to a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr, KI) and continuously add it during the formation of halogenated grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se, and Te, cyanates, thiocyanates, selenocyanates, carbonates,
Phosphate and acetate may be present.

The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization and reduction sensitization in any step of the silver halide emulsion production process. Can be applied with. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose. Generally preferred is when at least one chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan Company. Published, 1977
Year, (TH James, The Theoryof the Photographic Proc
ess, 4th ed, Macmillan, 1977) 67-76, and using active gelatin, or Research Disclosure 120, 19
1974, Apr. 2008; Research Disclosure, Vol. 34, Jun. 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,3. 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent No. 1,31.
PAg 5-10, pH as described in 5,755
5 to 8 and a temperature of 30 to 80 ° C., sulfur, selenium,
It can be tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom. In particular,
K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdC
l ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na
₂ PdCl ₆ or K ₂ PdBr ₄ are preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,05
The sulfur-containing compounds described in 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,
411,914, 3,554,757, JP-A-5
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 .

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mol of silver halide.
It is 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, more preferably 1
It is ^{x10 -5 to} 5x10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

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, a method of growing in a low pAg atmosphere of pAg1 to 7 called silver ripening, or a method of ripening, a pH of 8 to 11 called high pH ripening. Any method of growing or aging in a high pH atmosphere 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. Known reduction sensitizers include stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or 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 is suitable per mol of silver halide. The reduction sensitizer is dissolved in water or a 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 convert it into 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 ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. 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 (for example, NaBO ₂ · H ₂ O ₂ , 3H ₂ O, 2NaC).
_{O 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2N
a ₂ SO ₄ · H ₂ O ₂ · 2H ₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P)
₂ O ₈ ), a peroxy complex compound (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), permanganate (e.g., KMnO _4), chromates (e.g., K ₂ C
r ₂ O ₇ ) and other oxyacid salts, iodine and bromine and other halogen elements, perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferrate) and thio. There are sulfonates. Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is mentioned as an example.

The preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinones of 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 from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, 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, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
No. 47 and Japanese Patent Publication No. 52-28660 can be used. Japanese Patent Application Sho 6
There are compounds described in 2-47225. 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. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

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. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, 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 and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12,375, and JP-A-52. -110,618 and 52-109,925.

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.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-8-969 and 4,225,666.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation and can be added at any time during the formation of silver halide grains, including the method started in US Pat. No. 4,183,756. The addition amount is 4 × 10 ⁻⁶ to 1 mol of silver halide.
Although it can be used in an amount of 8 × 10 ⁻³ mol, in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective.

Regarding the various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same, Research Disclosure No. 308119 (19) is generally used.
1989) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Halogen that can be used in combination Page 147, line 26 to page 148, line 12 Silver emulsion 3) Yellow coupler page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; European Patent No. 421,453A1 Page 3, line 5 to page 25, line 55) Cyan coupler page 149, lines 29 to 33; European patent 432,804A2, page 3, line 28 to page 40, line 2 6) Polymer coupler, page 149, lines 34 to 38; European Patent 435,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler, page 53, line 42 to 137. Page 34 line, page 149 page 39 line -Line 45 to 8) Other functionality Page 7, line 1 to page 53, line 41, page 149, line 46, coupler line to page 150, line 3; European Patent 435,334A3, 3rd line Page 1 line 1 to page 29 line 50 9) Antiseptic and antifungal agent Page 150 line 25 to line 28 10) Formalin page 149 page 15 to line 17 scavenger 11) Other additives 153 Page 38, line 47 to line 47; European Patent No. 421,453A1, page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 12) Dispersion method 150 Page 4th line to 24th line 13) Support, page 150, 32nd line to 34th line 14) Film thickness and film physical properties, page 150, 35th line to 49th line 15) Color development, black and white, page 150, line 50 P. 151-p. 47 line; European special development / fog No. 442, 323A2, p. 34 line 11-line. 5th process No. 4, page 35, lines 14 to 22 16) Desilvering process page 151, line 48 to page 152, line 53 17) Automatic developing machine page 152, line 54 to page 153 2 Line 18) Washing / stabilization process, page 153, lines 3 to 37

[0134]

EXAMPLES The present invention will now be specifically described by way of examples, which should not be construed as limiting the invention.

Example 1 Preparation of Emulsion (1) Preparation of Emulsion A 0.7 g of potassium bromide, 0.4 g of oxidized gelatin, 4
0.1 liter of an aqueous solution containing 4 cc of nitric acid of N.
Add 19 g of BASF Pluronic TM-31R1 and stir at 45 ° C., 0.3 by double jet method.
The silver potential of −2.8 cc of an aqueous solution containing 7 g of silver nitrate and 2.8 cc of an aqueous solution of potassium bromide of 0.27 g was changed over 60 seconds to −.
It added, keeping at 40 mV (1st addition). After addition
An aqueous solution containing 0.5 g of potassium bromide was added, 9
The temperature was raised to 60 ° C over a period of minutes. Then 3.4
g ammonium sulfate and 2.5N NaOH aqueous solution 2
An aqueous ammonia solution containing 7.0 cc was added, and the mixture was further stirred for 9 minutes. Next, 95 cc of an aqueous solution containing 17 g of alkali-oxidized gelatin and 4N nitric acid of 10.8 cc
Was added over 2 minutes. Then, 7.5 cc of an aqueous solution containing 1.02 g of silver nitrate and 8.3 cc of 0.79 g of an aqueous potassium bromide solution were added over 5 minutes (second addition). Aqueous solution 475c containing 129 g of silver nitrate in 60 minutes
c and 95 g of an aqueous potassium bromide solution (475 cc) were added at an accelerated flow rate (the flow rate at the end was 10 times that at the start) (third addition). During this period, the addition amount of the potassium bromide solution was controlled so that the silver potential was kept at 0 mV. Next, 200 cc of an aqueous solution containing 3.9 g of potassium iodide was added over 2 minutes. Two minutes later, in 19 minutes 250 cc of an aqueous solution containing 68.8 g of silver nitrate and 50.3 g of an aqueous solution of potassium bromide 250.
cc was added while maintaining the silver potential at -30 mV (fourth addition). Thereafter, the emulsion was desalted by a conventional flocculation method, and at 40 ° C., pH = 6.5 and pAg = 8.5.
And then optimally chemically sensitized with sodium thiosulfate, chloroauric acid and potassium thiocyanate in the presence of sensitizing dyes S-6 and S-7 at 65 ° C. to obtain tabular silver iodobromide emulsion A.
(AgI content 2.0 mol%) was obtained. The obtained particles have an equivalent circle diameter of 2.0 μm and an average particle thickness of 0.18 μm.
m, the average aspect ratio was 11, the ratio of the projected area occupied by tabular grains having an aspect ratio of 2 or more was 99%, and the variation coefficient of the grain size distribution was 5%.

(2) Preparation of Emulsion B Emulsion B was prepared in the same manner as Emulsion A, except that the silver potential of (the fourth addition) in Emulsion A was changed to -50 mV.

(3) Preparation of Emulsion C Emulsion C was prepared in the same manner as Emulsion A, except that the silver potential of (the fourth addition) in Emulsion A was changed to -70 mV.

(4) Preparation of Emulsion D Emulsion D was prepared in the same manner as emulsion A except that various compounds shown in Table 2 were added.

(5) Preparation of Emulsions E to I Emulsions E to E were prepared in the same manner as in the preparation of Emulsion B except that various compounds shown in Table 2 were added.
I was prepared.

(6) Preparation of Emulsions J to L In Emulsion E, the silver potential of (fourth addition) was set to -8,
Emulsions J to L were prepared in exactly the same manner as the preparation of Emulsion E, except that they were set to 0 mV, -200 mV, and -250 mV. (7) Preparation of Emulsion M In Emulsion E, Pluronic TM-31 manufactured by BASF Corporation
Projection occupied by tabular grains having a circle equivalent diameter of 1.6 μm, an average grain thickness of 0.3 μm, an average aspect ratio of 5.3, and an aspect ratio of 2 or more, without adding R1 and adjusting the addition speed of the first addition. A tabular silver iodobromide emulsion M having an area ratio of 97% and a grain size distribution variation coefficient of 11% was prepared.

Preparation and Evaluation of Coated Samples Dodecylbenzene sulfonate as a coating aid, p-vinylbenzene sulfonate as a thickening agent, vinyl sulfone compound as a hardening agent, and
Then, a polyethylene oxide compound was added as a photographic property improving agent to prepare an emulsion coating solution. Subsequently, the coating solutions are separately and evenly coated on a polyester base which has been subjected to an undercoating treatment, and a surface protective layer mainly composed of an aqueous gelatin solution is coated thereon to obtain coating samples 101 to 113 having emulsions A to M, respectively. Was produced. With regard to Emulsions B and C, various compounds were added to the coating solution to obtain a coated sample 11
4,115 were produced. At this time, the samples 101 to 115
The coating amount of silver was 5.0 g / m ² , the gelatin coating amount of the protective layer was 1.3 g / m ² , and the gelatin coating amount of the emulsion layer was 2.7 g / m ² . Further, the time taken from the preparation of the emulsion to the start of coating was 4 hours.

The following experiments were conducted to evaluate the coated samples thus obtained. First, coated samples 101 to
Prepare two sets of 115 sample pieces, one set at 40 ° C 80% RH
Stored under conditions for 1 week, the other set was stored in the freezer as a control, 1/100 second exposure time, 10C
Wedge exposure was carried out with the exposure amount of MS, development was carried out at 20 ° C. for 4 minutes with a processing solution having the following composition, and then fixing, washing with water, drying, and sensitometry were carried out to measure fog and fog +
The sensitivity is calculated by the reciprocal of the exposure dose that gives a density of 0.1
The temporal stability of the coated material was evaluated.

Treatment liquid 1-Phenyl-3-pyrazolidone 0.5 g Hydroquinone 10 g Ethylenediaminetetraacetic acid-2-sodium 2 g Potassium sulfite 60 g Boric acid 4 g Potassium carbonate 20 g Sodium bromide 5 g Diethylene glycol 20 g Sodium hydroxide The pH was adjusted to 10.0 with water and 1 liter was obtained. The results are shown in Table 2 below.

[0144]

[Table 2]

From Table 2, the sample coated with the emulsion of the present invention has the same performance as the comparative sample in terms of sensitivity and fog, but the photographic performance after storage for 1 week at 40 ° C. and 80% RH was as follows. It can be seen that almost no increase in fog was observed, the change in sensitivity was small, and the stability of the coating solution over time was excellent. Further, in the sample in which the radical scavenger was added to the coating solution, no improvement was observed in the stability over time. Further, it can be seen that the monodisperse emulsion using Pluronic is more effective.

Example 2 Emulsions A to M prepared in Example 1 were stored at 5 ° C. and 25% RH (refrigerator) for 3 weeks, and then the same methods as those for coating samples 101 to 113 described in Example 1 were carried out. Then, the coated sample 201
~ 213 were produced. One piece of each of the coated samples 101 to 113 was stored in a freezer and subjected to the same exposure and development treatments as in Example 1 at the same time as the samples 201 to 213 to make a control. The results are shown in Table 3.

[0147]

[Table 3]

From Table 3, it can be seen that the emulsion of the present invention has a small change in performance during storage in a refrigerator and is excellent in production stability.

Example 3 To examine the performance stability of the emulsions A to M prepared in Example 1 in the coated state, after mixing with the coupler dispersion, 4
After stagnating for 10 minutes, 2 hours, 6 hours, and 10 hours at 0 ° C., Samples 301 to 352 were prepared in the same manner as in Example 1. Samples 301 to 352 produced in this way
Was subjected to the same exposure and development processing as in Example 1 to evaluate the performance fluctuation due to the stagnant coating liquid. Table 4 shows the results.

[0150]

[Table 4]

From Table 4, it was found that the sample of the present invention showed a remarkable improvement effect, with almost no fogging change and sensitivity change even after being stagnated in the coating solution at 40 ° C. for 10 hours.

Example 4 Preparation of Coating Sample 401 A sample 401 having the following basic constitution was formed on a 127 μm-thick cellulose triacetate film support which was undercoated. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.2 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic solvent Oil- 1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.4 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil -3 0.1 g Dye D-4 0.8 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06 µm, variation coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g Yellow colloidal silver Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red photosensitive emulsion layer Monodisperse cubic emulsion AA (average particle size 0.3 μm, size variation coefficient 12%, AgI content) Mol%) Silver amount 0.4 g Monodisperse cubic internal latent image type emulsion BB (average particle size 0.26 μm, size variation coefficient 8%, AgI content 3 mol%) Silver amount 0.2 g Gelatin 0.6 g Coupler C- 1 0.12 g Coupler C-2 0.05 g Coupler C-6 0.004 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Fifth Layer: Medium-speed red photosensitive emulsion layer Monodisperse tetradecahedral emulsion CC (average particle size 0.4 μm, size variation coefficient 14%, AgI content 4 mol%) Silver amount 0.5 g Gelatin 0.8 g Coupler C- 1 0.2 g Coupler C-2 0.05 g Coupler C-6 0.01 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: high-sensitivity red photosensitive emulsion layer Monodisperse plate Emulsion DD (Average grain size .6 μm, variation coefficient of size 12%, AgI content 2 mol%) Silver amount 0.4 g Gelatin 1.1 g Coupler C-3 0.7 g Coupler C-6 0.04 g Additive P-1 0.1 g Seventh layer : Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg High boiling organic solvent Oil-1 0.02 g Dye D-5 0.02 g Eighth layer: Intermediate layer Yellow colloidal silver Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g 9th layer: low-sensitivity green photosensitive emulsion layer Cubic emulsion EE (average grain) Diameter 0.2 μm, size variation coefficient 22%, AgI content 3 mol%) Silver amount 0.2 g Monodisperse cubic emulsion FF (average particle size 0.25 μm, size variation coefficient 13%, AgI content 3 mol%) Silver Amount 0.2g Monodisperse Cubic internal latent image type emulsion GG (average particle diameter 0.26 μm, size variation coefficient 8%, AgI content 3 mol%) silver amount 0.2 g gelatin 0.5 g coupler C-4 0.1 g coupler C-7 0. 05g Coupler C-8 0.2g Compound Cpd-B 0.03g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.04g Compound Cpd-J 10 mg Compound Cpd-L 0.02g High Boiling point organic solvent Oil-1 0.1 g High boiling point organic solvent Oil-2 0.1 g Tenth layer: medium-speed green photosensitive emulsion layer Monodisperse cubic emulsion HH (average particle size 0.4 μm, size variation coefficient 7%, AgI content 3 mol%) Silver amount 0.4 g Internally fogged silver iodobromide emulsion (average grain size 0.2 μm, size variation coefficient 14%, AgI content 1 mol%) Silver amount 0.04 g Zera 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-2 0.01 g 11th layer: high-sensitivity green photosensitive emulsion layer Monodisperse tabular emulsion II (average particle size 0.7 μm, size variation coefficient 18) %, AgI content 2 mol%) Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0 0.02 g Compound Cpd-F 0.04 g Compound Cpd-K 5 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 .02g 12th layer: Intermediate layer Gelatin 0.6g Compound Cpd-L 0.05g High boiling point organic solvent Oil-1 0.05g 13th layer: Yellow filter layer Yellow colloidal silver 0.07g Gelatin 1.1g Color mixing prevention Agent Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: low-sensitivity blue photosensitive emulsion layer Monodisperse Cubic emulsion JJ (average grain size 0.3 μm, size variation coefficient 18%, AgI content 3 mol%) Silver amount 0.2 g Monodisperse cubic emulsion KK (average grain size 0.4 μm, size variation coefficient 13%, AgI Content 3 mol%) Silver amount 0.3 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g Fifteenth layer: Medium speed blue photosensitive emulsion Monodisperse tabular emulsion LL (average grain size 0.6 μm, size variation coefficient 12%, AgI content 2.5 mol%) silver amount 0.4 g gelatin 0.9 g coupler C-5 0.1 g coupler C-60 1 g Coupler C-10 0.6 g 16th layer: High-sensitivity blue-sensitive emulsion layer Emulsion A described in Example 1 Silver amount 0.5 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0. 1 g Coupler C-10 0.6 g High boiling point organic solvent Oil-2 0.1 g 17th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber Agent U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g Eighteenth layer: second protective layer Colloidal silver Silver amount 0. 1g fine-grained odor Silver emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 19th layer: third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μm) 1 g Methyl methacrylate and acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3 mg Surfactant W-2 0.03 g Also, all In addition to the above composition, the additive F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added.

The sensitizing dye was added as shown in Table 5 immediately before the chemical sensitization of Emulsions AA to LL.

[0155]

[Table 5]

The compounds used are represented by the following "Chemical formula 30" to "Chemical formula 4".
3 ”.

[0157]

Embedded image

[0158]

[Chemical 31]

[0159]

Embedded image

[0160]

[Chemical 33]

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

[Chemical 38]

[0166]

[Chemical Formula 39]

[0167]

[Chemical 40]

[0168]

Embedded image

[0169]

Embedded image

[0170]

[Chemical 43]

Samples 402 to 413 were prepared in the same manner as Sample 401, except that Emulsion A to Emulsion B used in the 16th layer of Sample 401 (high-sensitivity blue-sensitive emulsion layer) were changed to Emulsions B to M.
The following evaluations were performed on Samples 401 to 413. First, two sets of sample pieces of the coated samples 401 to 413 were prepared, one set was stored under the conditions of 40 ° C. and 80% RH for one week, and the other set was stored in a freezer as a control, and the exposure time was 1/100 second. After the white light wedge exposure was applied with an exposure amount of 20 CMS, the following composition was processed and sensitometry was performed.

Development processing conditions: Processing step time Temperature First development 6 minutes 38 ° C. Water washing 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. Bleach 2 minutes 38 ° C. Bleach 6 minutes 38 ° C. Settling 4 minutes 38 ° C. Water washing 4 minutes 38 ° C. Final rinse 1 minute 25 ° C. The composition of each treatment solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g sodium bicarbonate 12 g 1-phenyl-4-methyl-4-hydroxymethyl 1.5 g-3-pyrazolidone potassium bromide 2.5 g potassium thiocyanate 1.2 g potassium iodide 2.0 mg diethylene glycol 13 g water 1000 ml pH 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide. [Reversal liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide. [Color developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate / dihydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with sulfuric acid or potassium hydroxide. [Pre-bleaching] Ethylenediamine tetraacetic acid / sodium salt / dihydrate 8.0 g Sodium sulfite 6.0 g 1-thioglycerol 0.4 g Formaldehyde sodium bisulfite adduct 30 g Water was added to 1000 ml pH 6.20 pH was Adjusted with acetic acid or sodium hydroxide. [Bleaching solution] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 2.0 g Ethylenediamine tetraacetic acid / Fe (III) / ammonium dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5 The .70 pH was adjusted with nitric acid or sodium hydroxide. [Fixer] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with acetic acid or aqueous ammonia. [Final rinse liquid] 1,2-benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Polymaleic acid (average molecular weight 2,000) 0.1 1000 ml pH 7.0 with addition of water The results obtained are shown in Table 6 below.

[0173]

[Table 6]

The color reversal density of the high-sensitivity blue-sensitive emulsion layer of the 16th layer was estimated based on the relative exposure amount which gives a density of 2.5 times the minimum yellow density, and the stability of the coated material with time was evaluated. . From Table 6, it can be seen that the sample in which the emulsion of the present invention was coated in the 16th layer (high-sensitivity blue-sensitive emulsion layer) had a small change in sensitivity with time of the coated material and was excellent in stability over time.

Example 5 1) Support The support used in the examples of the present invention was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin P.326 as an ultraviolet absorber.
(Manufactured by Ciba-Geigy Co.) 2 parts by weight are dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.0 times at 140 ° C., followed by 1
Lateral stretching of 3.0 times is performed at 30 ° C, and further 6 times at 250 ° C
It was heat set for 2 seconds to obtain a PEN film having a thickness of 90 μm.
Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours. 2) Coating of undercoat layer The above-mentioned support is subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides thereof,
An undercoat liquid having the following composition was applied to each surface, and an undercoat layer was provided on the high temperature surface side during stretching. Pillar Pill for corona discharge treatment
A 30 cm wide support is treated at 20 m / min using a solid state corona processor 6KVA model manufactured by ar. At this time, the object to be processed is 0.37 from the readings of current and voltage.
Processing of 5 KV · A · min / m ² was performed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The UV discharge treatment was performed while heating at 75 ° C. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode at 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 ml Sodium α-sulfo-di-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0.5 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g Aziridine 3-fold molar adduct of trimethylolpropane 0.2 g Trimethylolpropane-toluene diisocyanate 3-fold molar adduct 0.2 g Methanol 15 ml Acetone 85 ml Formaldehyde 0.01g Acetic acid 0.01g Concentrated hydrochloric acid 0.01g

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer, a magnetic recording layer and a slipping layer having the following compositions were coated as back layers. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, the precipitate was washed with water by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions have been removed is redispersed in 1500 parts by weight of water, and 650
The powder was sprayed in a firing furnace heated to 0 ° C. to obtain a bluish tin oxide-antimony oxide composite fine particle powder having an average particle size of 0.005 μm. The specific resistance of this fine particle powder was 5 Ω · cm. A mixed solution of 40 parts by weight of the above fine particle powder and 60 parts by weight of water was adjusted to pH 7.0 and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILLYA.BAC).
It was prepared by dispersing with a HOFENAG) until the residence time reached 30 minutes. The average particle size of the secondary aggregate at this time is about 0.
It was 04 μm.

3-1-2) Coating of conductive layer A conductive layer having the following formulation was coated so that the dry film thickness would be 0.2 μm, and dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion liquid prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight P-chlorophenol 0.5 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V), and it had an excellent antistatic property. 3-2) Coating of magnetic recording layer Magnetic substance Co- deposition γ-Fe ₂ O ₃ (long axis 0.14 μm, uniaxial 0.0
3 μm needle-shaped, specific surface area 41 m ² / g, saturation magnetization 89emu / g,
The surface is treated with 2% by weight of Fe ₂ O ₃ with aluminum oxide and silicon oxide respectively, coercive force 930 Oe, Fe ²⁺ / Fe ⁺³ ratio 6/94 1100 g, water 220 g and poly (polymerized) Once
6) 150 g of a silane coupling agent of oxyethylenepropyl trimethoxysilane was added and well kneaded for 3 hours in an open kneader. The coarsely dispersed viscous liquid was dried at 70 ° C. for one day, water was removed, and then 110
Surface-treated magnetic particles were produced by heating at ℃ for 1 hour. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

The above-mentioned surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Furthermore, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours. The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Furthermore, diacetyl cellulose and a 3-fold mole addition product of trimethylolpropane-toluene diisocyanate as a curing agent were added to the binder in an amount of 20 wt%. The liquid obtained was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity of the obtained liquid was about 80 cp. In addition, the coating is performed on the above conductive layer with a bar coater to give a film thickness of 1.2.
It was performed so as to have a thickness of μm. The amount of the magnetic substance was applied so as to be 62 mg / m ² . Further, silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive were added so as to be 10 mg / m ² . Drying is 11
It was carried out at 5 ° C for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C). When using a blue filter in Status M of X- write, increment of the color density of D ^B of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer is 4.2 emu / m ² , and the coercive force is 9
23Oe, the squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following prescription liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (compound a) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b) 9 mg / m ² Compound a / Compound b (6: 9) was xylene and propylene glycol monomethyl ether (volume ratio 1:
1) Heat and dissolve in a solvent at 105 ° C., and add 10 volumes of this solution to propylene glycol monomethyl ether (25
C.) to give a fine dispersion. After further diluting in 5-fold amount of acetone, it was redispersed with a high-pressure homogenizer (200 atm) to obtain a dispersion (average particle size 0.01 μm), which was then added and used. The performance of the obtained sliding layer is such that the dynamic friction coefficient is 0.06 (5 mmφ stainless hard ball, load 100).
g, speed 6 cm / minute), static friction coefficient 0.07 (clip method), and excellent properties. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

Next, the first layer to the nineteenth layer described in Example 4 were coated on the side opposite to the back layer obtained above.
Samples 501 to 510 corresponding to the samples 401 to 410 were created. When these samples 501 to 510 were evaluated by the evaluation method described in Example 4, the same effects as those described in Example 4 were observed.

[0182]

INDUSTRIAL APPLICABILITY As described in detail above, according to the present invention, a photographic emulsion capable of improving the production stability, such as excellent stability of the coating solution over time, stability of the coating solution and stability of the emulsion during refrigeration. Can be provided.

Claims (3)

[Claims] 1. At the time of emulsion preparation, -200 mV or more and -50 m
A method of producing a silver halide emulsion, which comprises a step of silver potential of V or less and contains a radical scavenger represented by the general formula [A] or [B]. Embedded image In the general formula [A], R and R ′ may be the same or different and each represents an alkyl group or an aryl group. In the general formula [B], R ₁ and R ₂ may be the same or different and each is a hydroxyamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, It represents an arylthio group, an alkyl group or an aryl group. 2. An emulsion preparation of -200 mV or more and -50 m
A method for producing a silver halide emulsion comprising a step of silver potential of V or less and containing a radical scavenger represented by the general formula [C]. Embedded image In the general formula [C], R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, It represents a sulfonyl group, a carboxyl group, a carbamoyl group, a sulfamoyl group, a halogen atom or -X-R _a0 . Here, -X- represents -O-, -S- or -N (R _a6 )-. R _a0 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _a6 represents a hydrogen atom or a group defined by R _a0 . R _{a1 to} R _a5
Of the above groups, the substituents in the ortho positions may be bonded to each other to form a 5- to 7-membered ring. However, each group of R _{a1 to} R _a5 is not a hydrogen atom at the same time, and when R _a3 is a halogen atom, —O—R _a0 or —S—R _a0 , at least one of R _{a1 and} R _a5 is It is an alkyl group. 3. A silver halide photographic light-sensitive material containing an emulsion according to the method for producing an emulsion according to claim 1, wherein the radical scavenger is added after desalting and dispersing.