JPH09197604A - Silver halide emulsion and photographic material using the emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion which is less fogging and high sensitive, and a photographic material using the emulsion. SOLUTION: In a silver halide emulsion prepared in a dispersion medium solution, nucleation, maturing or growth of silver halide particles are carried on in a dispersion medium containing gelatin having an amino group having a chemically decorated numerical rate of larger than 30% in the dispersion medium, and the silver halide emulsion is chemically sensitized, including selenium sensitization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion having less fog and high sensitivity, and a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more severe, and the demand for silver halide emulsions and light-sensitive materials with low fog and high sensitivity has been increasing. The silver halide emulsion used in the silver halide photographic light-sensitive material is usually chemically sensitized with various chemical substances in order to obtain desired sensitivity, gradation and the like. As typical methods, various methods of sensitization by sulfur sensitization, selenium sensitization, sensitization of noble metals such as gold, reduction sensitization, and a combination thereof are known.

In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, as well as rapid processing in which development progress has been accelerated. It has been done.

Among the above-mentioned sensitizing methods, the selenium sensitizing method is described in US Pat. No. 1,574,944, No. 1,602,592.
No. 1623499, No. 3297446, No. 3297447, No. 3320069, No. 34.
No. 08196, No. 3408197, No. 34426.
No. 53, No. 3420670, No. 3591385
, French Patent Nos. 2693038 and 20932
09, Japanese Patent Publication Nos. 52-34491 and 52-3449.
No. 2, No. 53-295, No. 57-22090, JP-A Nos. 59-180536, 59-185330, 59-181337, 59-187338 and 5
Nos. 9-192241, 60-150046, 60
-151637, 61-246738, British Patents 255846, 861984, and H.M. E. FIG.
Spencer et al., Junalof Photog
raphic Science, Vol. 31, 158-1
It is disclosed on page 69 (1983). In general, selenium sensitization has a greater sensitizing effect than sulfur sensitization that is usually performed in the art, but it tends to cause fogging and tend to be softened. Many of the above known patents improve on these disadvantages,
Insufficient results have yet been obtained, and there has been a keen need for fundamental improvements, especially for suppressing fogging. The selenium sensitizer represented by the general formula 1 is disclosed in JP-A-7-140.
579, it has been shown that it can be a selenium sensitizer with low fog and high sensitivity, but these compounds are not yet sufficient, and the fog can be suppressed to a low level, and a silver halide emulsion having a high sensitivity can be obtained. Was desired.

With respect to chemically modified gelatin, as shown in JP-A-62-157024, the gelatin which has been subjected to oxidation treatment is thinner than non-oxidized gelatin by controlling the methionine content. It has been shown that particles are formed. European patent 51474
No. 2A shows a method of forming particles in the presence of the oxidized gelatin and a polyalkylene compound. Further, it is well known that selenium sensitization is carried out on the precipitated emulsion by adding gelatin having a --NH ₂ group reduced by phthalation at the time of precipitation. However, in such a case, the phthalated gelatin is used only after washing the silver halide emulsion with water, and it is different from the emulsion formed by using the phthalated gelatin during grain formation, ripening or growth as in the present invention. Is completely different, and a system in which nucleation, ripening, or growth of grains that have been chemically sensitized, including selenium sensitization, is known in a dispersion medium containing gelatin chemically modified with -NH ₂ groups is known. It was difficult to predict the result.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide emulsion having less fog and high sensitivity, and a silver halide photographic light-sensitive material using the same.

[0007]

The object of the present invention has been achieved by the following items: (1) In a silver halide emulsion formed in a dispersion medium solution, the number of chemically modified --NH ₂ groups of the dispersion medium. A chemistry in which nucleation, ripening or growth of the silver halide grains are carried out in a dispersion medium containing gelatin, the proportion of which is 30% or more, and the silver halide emulsion contains at least selenium sensitization. A silver halide emulsion characterized by being sensitized. (2) A seed crystal formed by nucleation, ripening, or growing of silver halide grains in a dispersion medium is characterized in that the ratio of the number of chemically modified --NH ₂ groups in the dispersion medium is 30% or more. A silver halide photographic emulsion characterized by being chemically sensitized, including selenium sensitization, in a photographic emulsion containing silver halide grains obtained by using and growing. (3) A selenium sensitizer represented by the following general formula (I), which is selenium sensitized (1) or (2)
Silver halide emulsion of the general formula (I)

[0008]

Embedded image

In the formula, Z ₁ is a hydrogen atom, an aliphatic hydrocarbon group,
An aryl group, a heterocyclic group, OR ₁ , N (R ₂ ) R ₃ is represented, Z ₂ is an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, R ₁ , R ₂ , and R ₃ are hydrogen atoms, It represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. (4) The silver halide emulsion of (1) to (3), which is subjected to reduction sensitization in the process of forming silver halide grains. (5) At least one silver halide emulsion layer on a support. A silver halide photographic light-sensitive material having the above-mentioned is characterized by containing at least one silver halide emulsion (1) to (4) among the light-sensitive silver halide emulsions contained in the silver halide emulsion layer. Silver halide photographic light-sensitive material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The gelatin whose -NH ₂ group is chemically modified (hereinafter referred to as modified gelatin) used in the present invention will be described. As the -NH ₂ group in gelatin, the amino group of the terminal group of the gelatin molecule, lysine group, hydroxylysine group, histidine group, the amino group of arginine group, and the amino group if the arginine group is converted to the ornithine group. Can be mentioned. Furthermore, impurity groups such as adenine and guanine groups can also be mentioned. The chemical modification of —NH ₂ group means adding a reaction reagent to gelatin and reacting with the amino group to form a covalent bond or deamination. That is, a primary amino group (-
It shows that NH ₂ ) is converted to a secondary amino group (—NH—), a tertiary amino group or a deamination product. Specifically, for example, acid anhydrides (maleic anhydride, o- phthalic anhydride, succinic anhydride, isatoic anhydride, benzoic anhydride, etc.), acid halide (R-COX, R-SO 2, R
-O-COX, such as Phenyl-COCl), a compound having an aldehyde group (R-CHO, etc.), compounds having an epoxy group, deamination base (HNO _2, deaminase, etc.), active ester compounds (sulfonic acid ester, p -Nitrophenyl acetate, isopropenyl acetate, methyl o
-Chlorobenzoate, p-nitrophenylbenzoate, etc.), isocyanate compound [Aryl halide (benzyl b
romide, biphenyl-halomethanes, benzoyl halomethane,
phenyl benzoylalo-methane. 1-Fluoro-2,4-dinitro-b
enzene), β-kotohalide, α-haloaliphatic acid, β-hal
onitrile, (s-triazine, pyrimidine, pyridazine, pyrazi
ne, pyridazone, quinoxaline, quinazoline, phthalazine,
benzoxazole, benzothiazole, benzoimidazole), carbamoylating agents (cyanate, nitruurea)
Etc.), compounds having an acrylic type active double bond group (male
imide, acrylamine, acrylamide, acrylonitrile, methlmet
haacrylate, vinyl, sulphone, vinilsulphonate ester, su
lphonamode, styrene and vinylpyridine, allylamime, bu
tadiene, isoprene, chliroprene, etc.), sultones (buta
ne sultone, propane sultone) guanidine agent (o-meth
ylisourea etc.), carboxylazine etc., and the reaction can be achieved.

In this case, the gelatin --OH group or --COOH
A reagent that reacts mainly with the -NH ₂ group of gelatin is more preferable than a reagent that also reacts with a group to form a covalent bond. −
The proportion of reaction with NH ₂ is 30% or more, preferably 60% to 100%, and more preferably 95 to 100. Further, the reaction product has a group in which oxygen of an ether or ketone group is replaced with chalcogen (for example, -S-,
More preferred is an embodiment which does not substantially contain a thione group). Here, "not substantially containing" means preferably 10% or less, and more preferably 0 to 3% of the number of chemically modified groups. Therefore, of the above, acid anhydrides, sultones, compounds having an active double bond group, carbamoylating agents, active halogen compounds, isocyanate compounds, active ester compounds, compounds having an aldehyde, and deamino groups are more preferable.
It is more preferable that the chemical modification does not substantially allow crosslinking between gelatin molecules. The term "substantially impossible" means preferably 10% or less of the chemically modified group,
3% is more preferable.

Other details of the chemical modifying agent and the method for chemically modifying gelatin are described in the following references, JP-A-4-4-2.
26449, Japanese Patent Laid-Open No. 50-3329, and US Pat. No. 252.
No. 5753, No. 2614928, No. 2614929
No. 275639, No. 2594293, No. 31
No. 32945, edited by Abiko Yoshihiro, glue and gelatin, No. II
Chapter, Japanese Niwa-Gelatin Industry Association (1987), Wa
The description in rd et al., The Science and Technology of Gelatin, Chapter 7, Academic Press (1977) can be referred to. Chemical modification% of the -NH ₂ group of the modified gelatin
Can be calculated as follows. The unmodified gelatin and the modified gelatin are prepared, and the -NH _{2 group} numbers of both are determined as e ₁ and e ₂ . The chemical modification% can be calculated from 100 × (e ₁ −e ₂ ) / e ₁ . Examples of the method for obtaining e ₁ and e ₂ include infrared absorption intensity based on —NH ₂ , NMR signal intensity of the proton, and a method utilizing a color reaction and a fluorescence reaction. For details, see Analytical Chemistry Handbook, The description in Organic Edition-2, Maruzen (1991) can be referred to. Other examples include changes in the titration curve of gelatin and quantitative methods such as the formol titration method. For details, see The Science and Technology of Gelatin, 15th.
The description in Chapter, Academic Press (1977) can be referred to. Other glutaraldehyde yo Britton-Robi
A method in which a mixture of nson high pH buffer is added to a gelatin solution of a specified concentration to develop color, and the spectral absorption intensity near 450 nm is measured and colorimetrically determined (Photographic G
elatin II, p. 297-315 Acadimic Press (1
976) can be referred to)

In the present invention, the modified gelatin is preferably used by the following method. (1) Nucleation and ripening are performed using a dispersion medium other than the modified gelatin (hereinafter referred to as unmodified gelatin), 10 to 99.7% by weight of the unmodified gelatin is removed before growth, and the modified gelatin is newly added. how to. (2) Nucleation is performed using unmodified gelatin, and after the nucleation, 10 to 9 of the modified gelatin is used.
A method of removing 9.5% by weight and newly adding the modified gelatin. (3) A method in which nucleation is performed at a low concentration of unmodified gelatin, and the modified gelatin is added after nucleation. (4)
Method of performing nucleation and ripening at a low concentration of modified gelatin and adding the modified gelatin after ripening (5) Method of performing nucleation and ripening at the concentration of the modified gelatin, after nucleation, or after ripening Modified gelatin can also be added.
(6) A method in which nucleation is performed or ripening is performed in the presence of unmodified gelatin, and then the gelatin is modified with the above-mentioned modifying agent to increase the ratio of the modified gelatin.
(7) Add non-modified gelatin until after nucleation or after ripening, homogenize and then modify the gelatin with the aforementioned modifier, homogenize and mix, and then use the modifier described below. A method of modifying gelatin and increasing the ratio of the modified gelatin. (8) Nucleation and ripening are performed in the presence of unmodified gelatin, and the modified gelatin is added during growth (9) Nucleation and ripening are performed in the presence of unmodified gelatin to grow A method of increasing the ratio of the modified gelatin by modifying the non-modified gelatin with the aforementioned modifying agent in the middle of the step. (10) A method in which the particles formed in (1) to (9) are used as seed crystals and grown in the presence of the modified gelatin or unmodified gelatin. (11) Seed crystals obtained by nucleation, ripening, and growing in the presence of unmodified gelatin until halfway through,
A method of further growing in the presence of the modified gelatin.

The present invention is characterized in that the modified gelatin is used during nucleation, ripening, or growth of silver halide grains, which is completely different from the conventional method used after sedimentation and washing with water. The effect of the present invention is not seen in the conventional method of using the modified gelatin after sedimentation and washing with water.

The following methods can be mentioned as the method of removing the dispersion medium. (1) A method of centrifuging a silver halide emulsion and removing a supernatant. (2) A method of removing by an ultrafiltration method using an ultrafiltration membrane. (3) A method of washing with settling water using an aggregating settling agent, or a method used in combination with a centrifugal separation method. The removal rate of the dispersion medium is preferably 10 to 99.7% by weight, more preferably 60 to 99%, still more preferably 90 to 99%. The low concentrations of (3) and (4) indicate 0.01 to 1% by weight, preferably 0.03 to 0.6% by weight, and more preferably 0.03 to 0.3% by weight. Further, the amount of modified gelatin added later is the amount necessary to achieve the embodiment of the present invention.

The amount of the modified gelatin in the dispersion medium in the present invention may be within the range where this effect is exhibited in the nucleation, ripening and growth stages, and the amount is the proportion of modification of the modified gelatin and the nucleation, ripening and growth. Depending on the stage of using the modified gelatin in the above, in the growth process, the modified gelatin is 30 to 100% by weight, preferably 40 to 100% by weight, and more preferably 50% to 100% by weight in all the gelatin in the total dispersion medium. It is preferably in the weight%.

The selenium sensitizer used in the present invention will be described. The selenium sensitizer used in the present invention,
The selenium compounds disclosed in conventionally known patents can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489,
It is preferable to use the compounds described in Japanese Patent Application Nos. 2-130976 and 2-229300. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2
-Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on.

Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, Japanese Patent Publication Nos. 46-4553 and 52-34.
No. 492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. When a non-unstable selenium compound is used, the non-unstable selenium compound can be changed to a labile selenium compound by a metal or a nucleophile.

In the present invention, among these selenium compounds, those represented by the general formula (I) shown below and the general formula (II) shown below, or the general formula (III) shown below are used. And the effect of the present invention is remarkable. Of these, when the compound represented by the general formula (I) is used, the effects of the present invention are particularly remarkable. General formula (I)

[0021]

Embedded image

In the formula, Z ₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, OR ₁ or N (R ₂ ) R ₃ , and Z ₂ represents an aliphatic hydrocarbon group, an aryl group, It represents a heterocyclic group, and R ₁ , R ₂ and R ₃ represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Next, the compound represented by formula (I) will be described in detail. In the general formula (I), Z ₁ , Z ₂ , R ₁ , R ₂ and R
_The aliphatic hydrocarbon group represented by ₃ preferably has 1 carbon atom.
To 30 and particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Here, the branched ones may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include, for example, methyl group, ethyl group, isopropyl group, t-
Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl And the like.

In the general formula (I), Z ₁ , Z ₂ ,
The aryl group represented by R ₁ , R ₂ and R ₃ preferably has 6 to 30 carbon atoms, particularly 6 to 2 carbon atoms.
It is a monocyclic or condensed ring aryl group of 0, and examples thereof include a phenyl group and a naphthyl group. In the general formula (I), Z
_The heterocyclic group represented by ₁ , Z ₂ , R ₁ , R ₂ and R ₃ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a base. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, for example, pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, thienyl group. , A furyl group, a benzothiazolyl group and the like. In the formula (I), each group represented by Z ₁ , Z ₂ , R ₁ , R ₂ and R ₃ may be substituted. Examples of the substituent include the following.

Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group,
Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl Group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group, etc.), heterocyclic group ( For example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 2-naphthyloxy group, etc.) ), An amino group (for example, an unsubstituted amino group, a dimethylamino group, an ethylamino group, an anilino group, etc.), Shiruamino group (e.g., acetylamino group, benzoylamino group, etc.), a ureido group (e.g., unsubstituted ureido group, N- methylureido group, N-
Phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group) , N, N-
Dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfonyl group (eg, mesyl group, A sulfinyl group (eg, a methylsulfinyl group, a phenylsulfinyl group, etc.), an alkyloxycarbonyl group (eg, a methoxycarbonyl group,
Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), acyloxy group (eg, acetoxy group, benzoyloxy group, etc.) ), A phosphoric acid amide group (eg, N, N-diethylphosphoric acid amide group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), a cyano group,
Examples include a sulfo group, a carboxy group, a hydroxy group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group (eg, a trimethylammonio group), a phosphonio group, a hydrazino group, and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), Z ₁ represents an aliphatic hydrocarbon group, an aryl group or N (R ₂ ) R ₃ , Z ₂ represents an aliphatic hydrocarbon group or a heterocyclic group, and R ₂ and R ₃ represents an aliphatic hydrocarbon group or an aryl group. In formula (I), Z ₁ more preferably represents an aliphatic hydrocarbon group or an aryl group, and Z ₂ represents an aliphatic hydrocarbon group having an electron-withdrawing group at the β-position or a heterocyclic group. Here, the electron-withdrawing group is Taft's substituent constant σ ^* value (Taft, RW, J
r. "Steric Effect in Organic Chemistry", John Wil
ey, New York (1956) pp 556-675. ) Represents a substituent of 0.50 or more. Examples of the electron-withdrawing group include a cyano group, a sulfonyl group, an acyl group, an oxycarbonyl group, a carbamoyl group, a phenyl group and a pentafluorophenyl group. The electron withdrawing group is more preferably a substituent having a Taft substituent constant σ ^* value of 1.50 or more. Specific examples of the aliphatic hydrocarbon group having an electron-withdrawing group at the β-position include 3-oxocyclohexyl group, 2-cyanoethyl group, 2-alkoxycarbonylethyl group, 2-alkylsulfonylethyl group and the like. General formula (II)

[0026]

Embedded image

In the formula, Z ₃ and Z ₄ may be the same or different, and are an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl). , An aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), a heterocyclic group ( For example, pyridyl, thienyl, furyl, imidazolyl),-
It represents NR ₄ (R ₅ ), —OR ₆ or —SR ₇ .

R ₄ , R ₅ , R ₆ and R _{7, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₃ .

However, R ₄ and R ₅ are hydrogen atoms or acyl groups (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) may be used.

In the general formula (II), preferably Z ₃ represents an alkyl group, an aryl group or —NR ₁ (R ₅ ), and Z ₄
Represents -NR ₈ (R _9). R ₄ , R ₅ , R ₈ and R
₉ may be the same or different, and a hydrogen atom,
It represents an alkyl group, an aryl group, or an acyl group.

In the general formula (II), more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenourea, tetraalkyl selenourea,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide. General formula (III)

[0032]

Embedded image

In the general formula (III), Z ₅ , Z ₆ and Z ₇ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₁₀ , -NR ₁₁ (R ₁₂ ), -SR
₁₃ , -SeR ₁₄ X, represents a hydrogen atom.

R ₁₀ , R ₁₃ and R ₁₄ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (III), Z ₅ , Z ₆ ,
The aliphatic group represented by Z ₇ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aralkyl group (for example, methyl,
Ethyl, n-propyl, isopropyl, t-butyl, n
-Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (III), Z ₅ , Z ₆ ,
The aromatic group represented by Z ₇ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a monocyclic or condensed ring aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3
-Sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (III), Z ₅ , Z ₆ ,
The heterocyclic group represented by Z ₇ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

In the general formula (III), the cations represented by R ₁₀ , R ₁₃ and R ₁₄ represent an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula (III), Z ₅ , Z ₆ or Z ₇ preferably represents an aliphatic group, an aromatic group or -0R ₁₀ ,
R ₁₀ represents an aliphatic group or an aromatic group.

Of the compounds represented by the general formula (III), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferred.

General formulas (I) and (II) are shown in the following chemical formulas 6 to 25.
Specific examples of the compounds represented by and (III) are shown below, but the invention is not limited thereto.

[0042]

[Chemical 6]

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

[Chemical 21]

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3,297,446, No. 3,297,447
No. 3320069, No. 3408196, No. 3408197, No. 3442553, No. 34
No. 20670, No. 3591385, French Patent Nos. 2693038 and 2093209, Japanese Patent Publication No. 52
-34491, 52-34492, 53-29
No. 5, 57-22090, JP-A-59-18053.
No. 6, No. 59-185330, No. 59-181337
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
Japanese Patent Application Nos. 1-287380, 1-250950, 1-2254441, 2-334090 and 2-11
No. 0558, No. 2-130976, No. 2-139918
Nos. 3, 229,300 and British Patent 255
No. 846, No. 861984, and H.M. E. FIG. Spen
cer et al., Journal of Photogra
phic Science Magazine, Volume 31, 158-169
Page (1983).

These selenium sensitizers are water or methanol.
Or an organic solvent such as ethanol and the like, or dissolved in a mixed solvent, or Japanese Patent Application Nos. 2-264447 and 2-26.
No. 4448, added during chemical sensitization.
Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one, and two or more of the above-described selenium sensitizers can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
Preferably, it is at least 1 × 10 ⁻⁸ mol per mol of silver halide. More preferably 1 × 10 ^-7 mol or more and 1 × 10
^-5 mol or less. The temperature for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or more and 80 ° C. or less. pAg and pH are optional. For example, the effects of the present invention can be obtained in a wide pH range of 4 to 9.

We have obtained high sensitivity, low fog, and gradation that have not been seen in the past by sensitizing grains using gelatin chemically modified with --NH ₂ by the conventional method. Considering the conditions of chemical sensitization to optimize the chemical sensitization of a certain grain, fog occurs due to excessive chemical sensitization for other grains, or chemical sensitization becomes insufficient due to insufficient chemical sensitization. It was thought that it was impossible to obtain an emulsion having high feeling, high contrast and low fog. On the other hand, the particles using gelatin chemically modified with -NH ₂ have a narrow inter-particle distribution of chemical sensitization, and it is considered that the chemical sensitization is performed more uniformly. Further, it can be understood that this effect exhibits a surprising effect on selenium sensitization because the distribution of selenium sensitized particles is easily attached.

Selenium sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include U.S. Pat.
Nos. 271,157, 3,531,289, 3,574,628, JP-A-54-1019, and 5
(A) Organic thioer described in 4-158917, etc.
Tellers, JP-A Nos. 53-82408 and 55-7773.
(B) thiourea derivatives described in JP-A Nos. 7-55-2982, etc .; and (c) thiocarbonyl groups sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent having
(D) imidazoles described in -100717,
(E) sulfite, (f) thiocyanate and the like.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, it is preferably 1 × per mol of silver halide.
It is at least 10 ^-4 mol and at most 1 × 10 ^-2 mol.

In the present invention, it is more preferable to simultaneously perform selenium sensitization, sulfur sensitization, gold sensitization and tellurium sensitization.

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

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

For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-
Toluenethiosulfonate, rhodanine and the like can be mentioned. Other U.S. Pat. Nos. 1,574,944 and 2,
Nos. 410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955, German Patent 1,42.
No. 2,869, JP-B-56-24937, and JP-A-55-55.
Sulfur sensitizers described in -45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount is
It varies over a considerable range under various conditions such as pH, temperature and the size of silver halide grains, but is preferably from 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. .

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. . Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of the gold sensitizer to be added varies depending on various conditions, but as a guide, it is preferably from 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁵ mol per mol of silver halide.

In chemical ripening, there is no particular limitation on the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. There is no need to provide it,
For example, the compound can be added at the same time as the initial stage (preferably) of chemical ripening or during the progress of chemical ripening, or at a different time. In addition, the compound may be added by dissolving the above compound in water or an organic solvent miscible with water, for example, a single solution or a mixed solution of methanol, ethanol, acetone or the like.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a pAg 1 to 7 low pAg atmosphere called silver ripening, or a method of ripening, and a method of high pH ripening called pH ripening of 8 to 8. Either the method of growing in a high pH atmosphere of 11 or the method of ripening 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, for example, stannous salts, 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, and two or more compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof 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 an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

The following is a description of the emulsion of the present invention and emulsions other than the present invention which are used in combination therewith. The silver halide grains used in the present invention are silver bromide, silver chloride,
Silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chloroiodobromide. Other silver salts such as silver rhodan, 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. The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-60-143331, JP-A-6-143331
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. In addition to a simple structure, a triple structure as disclosed in Japanese Patent Application Laid-Open No. 60-222844, or a multilayer structure of more than that, or a different composition on the surface of a core-shell double structure particle Or a thin silver halide having the following formula: In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. Examples of these are disclosed in JP-A-59-133.
540, JP-A-58-108526, European Patent No. 1
99,290A2, JP-B-58-24772, and JP-A-59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform with respect to the halogen composition or the core crystal.
Even those having a shell type structure can be formed. In the case of a joint structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a joint structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding 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. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment. In the case of silver halide grains in which two or more silver halides exist as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. A method for measuring the halogen composition distribution between grains is disclosed in JP-A-60-2.
No. 54032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. 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 silver iodide content near the surface,
Alternatively, increasing the silver chloride content can be selected according to the purpose because the adsorption property of the dye and the developing speed are changed.
When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, (100) plane and (1
11) The case where the halogen composition is changed only on one side of a tetrahedral grain composed of planes, or the halogen composition on one of the main plane and the side face of the tabular grain is changed.

The silver halide grains used in the emulsion of the present invention and the emulsions other than the present invention which are used in combination with the emulsion of the present invention, even if it is a normal crystal having no twin plane, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, and Silver Salt Photograph ( Corona), P. 163, such as a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a non-parallel with two or more non-parallel twin planes It can be selected from multiple twins or the like depending on the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, an octahedron consisting of (111) planes, Japanese Patent Publication No. 55-42737,
A dodecahedral particle having a (110) plane disclosed in JP-A-222842 can be used. In addition, Jou
rnal of ImagingScience 30
Volume 247 pages (h11) plane particles typified by (211) as reported in 1986, (331)
(Hh1) plane particles representing (210) plane, (hk0) plane particles representing (210) plane, and (hk) plane representing (321) plane.
1) The surface particles also need to be devised in the preparation method, but can be selected and used according to the purpose. A tetrahedral particle in which (100) plane and (111) plane coexist in one particle, a particle in which (100) plane and (110) plane coexist, or a particle in which (111) plane and (110) plane coexist, Particles in which two faces or many faces 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. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described by Cleeve in "Theory and Practice of Photography"
ry and Practice (1930)), 13
Page 1: Gatov, Photographic Science and Engineering (Gutoff, Photogr
aphic Science and Engineer
ring, Vol. 14, pp. 248-257 (1970)
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,4
It can be prepared by the method described in 39,520 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 sensitizing efficiency by a sensitizing dye, which are described in detail in US Pat. No. 4,434,226 cited above. 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. It is more preferably 2 or more and less than 30 and particularly preferably 3 or more and less than 25. The shape of the tabular grains can be selected from triangles, hexagons, and circles. U.S. Pat. No. 4,797,35
A regular hexagon having six sides of approximately the same length as described in No. 4 is a preferred form.

The equivalent circle diameter of tabular grains is 0.15 to 5.0.
μm is preferred. The thickness of the tabular grains is preferably from 0.05 to 1.0 μm. 0.05
If it is less than μm, the pressure property is undesirably deteriorated. 1.0 μm
If it exceeds 90, it is not preferable because the advantages of tabular grains cannot be fully utilized.

The proportion of tabular grains is preferably 50% or more, more preferably 80%, particularly preferably 90% of the total projected area of tabular grains having an aspect ratio of 3 or more.
% Or more. When monodisperse tabular grains are used, more preferable results may be obtained. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-15161.
According to the description of No. 8, etc., but briefly describing its shape,
70% or more of the total projected area of the silver halide grains is a hexagon in which the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less, and The hexagonal tabular silver halide grains are occupied by tabular silver halide grains having two parallel surfaces as outer surfaces. Variation (standard deviation)
(Value divided by the average particle size) is 20% or less.

It is also preferable to use particles having dislocation lines. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select a dislocation or a dislocation that is introduced linearly with respect to a specific direction of the crystal orientation of the grain, or to introduce the entire grain, or to introduce only a specific portion of the grain, for example. The dislocation can be introduced only in the fringe portion of the particle. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle. The silver halide emulsion used in the present invention is disclosed in European Patent Nos. 96,727B1 and 64,4.
No. 12,306,447C, for example, a treatment for rounding particles as disclosed in US Pat.
2, the surface may be modified as disclosed in JP-A-60-221320. Although a structure having a flat particle surface is generally used, it is sometimes preferable to form irregularities intentionally. JP-A-58-106532 and JP-A-60-221320 disclose a method of forming a hole in a part of a crystal, for example, a vertex or a center of a plane, or a method described in US Pat. No. 4,643,966. Raffle particles are an example.

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. Ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm can be selected and used. Preferably, grains having a size of 0.1 μm or more and 3 μm or less are used as photosensitive silver halide grains. The normal crystal 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, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a sphere equivalent diameter of a volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% to 3%, more preferably 20% to 3%, and still more preferably 15% to 3%. A monodisperse emulsion may be defined as having a grain size distribution such that 80% to 100% of all grains fall within ± 30% of the average grain size by number or weight of grains. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed 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 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 emulsion of the present invention and the photographic emulsions other than the present invention which are used in combination therewith are described in Graphide, "Physics and Chemistry of Photographs", published by Pol Montell (P. Glafkides,
Chemie et Physique Photog
raphique, Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographi).
c Emulsion Chemistry (Foca
1 Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL.
Zelikman et al. , Making an
d Coating Photographic Em
ulsion, 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 halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, 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 nearly uniform grain size can be obtained.

A method of adding silver halide grains which have been preliminarily formed into a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. The method described in 1. is optionally preferred. These can be used as seed crystals,
It is also effective when 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 the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface. A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in U.S. Pat. Nos. 3,477,852 and 4,1.
No. 42,900, European Patent 273,429, No. 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously. As a method of grain growth, in addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,4
No. 80, U.S. Pat. Nos. 3,650,757 and 4,2
The particle formation method of varying the concentration or varying the flow rate as described in US Pat. No. 42,445 is a preferred method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be 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. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is. A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in U.S. Pat.
No. 6,287, No. 3,342,605, No. 3,4
No. 15,650, 3,785,777, West German Patent Publication 2,556,885, and 2,555,364. Silver halide solvents are useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and the halide salt, or can be added together with the halide salt, the silver salt or the deflocculant. Can also be introduced. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps. As the ripening agent, for example, ammonia, thiocyanate (eg, rhodan potassium, rhodan ammonium), organic thioether compound (eg, US Pat. Nos. 3,574,628 and 3,021,215)
No. 3,057,724 and 3,038,80
No. 5, No. 4,276,374, No. 4,297,4
No. 39, No. 3,704, 130, No. 4,782
No. 013 and JP-A-57-104926. ), Thione compounds (for example, JP-A-53-8240)
No. 8, No. 55-77737, U.S. Pat.
No. 863, compounds described in JP-A-53-144319) and the growth of silver halide grains described in JP-A-57-202531. Mercapto compounds and amine compounds (for example, JP-A-54-100717). The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but it is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method of washing can be selected from the group consisting of a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. The coagulation sedimentation method 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, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before completion of chemical sensitization. A method of doping the entire grain and a method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. For example, Mg, Ca, Sr, Ba,
Al, Sc, Y, La, Cr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, and Bi 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, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , P
b (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe
(CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃
IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (C
N) ₆ . The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding a hydrogen halide aqueous solution (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, a water-soluble silver salt (for example, AgNO ₃ ) or an aqueous alkali halide solution (for example, NaCl, K
(Br, KI) can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions formed here may form a sparingly water-soluble silver salt such as silver halide, silver sulfide, or silver selenide, or a silver salt easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. As the inorganic oxidizing agent, for example, ozone, hydrogen peroxide and its adduct (eg, NaBO ₂
・ H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 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 ) and peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3
_{H 2 O, 4K 2 SO 4} · Ti (O 2) OH · SO 4 · 2
H ₂ O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] ・ 6H
₂ O), permanganates (eg KMnO ₄ ), chromates (eg K ₂ Cr ₂ O ₇ ), oxyacid salts,
There are halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high valent metals (eg potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidant, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonate and organic oxidizing agents of quinones.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation 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, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles. , Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as titraazaindenes and pentaazaindenes;
Many compounds can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-21.
2932. Antifoggants and stabilizers are used at various times before, during and 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 according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, 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. 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 nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, ie, for example, indolenine nuclei, benzoindolenine nuclei, indole nuclei, benzoxador nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei, quinoline nuclei are applied. it can. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- or 6-membered heterocyclic nucleus of 2,4-dione nucleus, rhodanine nucleus, or 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. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898, No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

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 sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat. No. 3,628,969.
JP-A-58-113928, that spectral sensitization is carried out simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, or the spectral sensitization can be started before the completion of silver halide grain precipitation. 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 is also possible to add it after the feeling, and it is possible to add it after the sensation.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756.

The addition amount is 4 × per mol of silver halide.
Although it can be used in an amount of 10 ^-6 to 8 × 10 ^-3 mol, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is effective when the silver halide grain size is more preferably 0.2 to 1.2 μm. is there.

A light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support. It suffices that at least one layer is provided, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. The arrangement of layers is, in order from the support side, a red-sensitive layer,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler and a DIR compound as described in JP-A-61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) / high-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / R
H / RL, or BH / BL / GH / GL / RL /
They can be installed in the order of RH.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of Japanese Patent No. 6, the blue-sensitive layer / GL / RL / GH / RH can be provided in this order from the farthest side from the support.

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

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above.

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

The above-mentioned various additives are used in the light-sensitive material of the present invention, but various additives other than the above can be used depending on the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 308119 (December 1989), and the relevant portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer same as above 3 Spectral sensitizer, page 23 to page 648 right column ~ 996 right to 998 right strong color Sensitizer 649 Page right column 4 Brightener page 24 647 Page right column 998 Right 5 Antifoggant, page 24 to 25 649 Page right column 998 Right to 1000 Right and stabilizer 6 Light absorber, page 25 to 26 649 Page right column to 1003 left to 1003 right Filter-dye, page 650 Left column UV absorber 7 Anti-staining agent page 25 Right column 650 Left to right column 1002 right 8 Dye image stabilizer page 25 1002 right 9 Hardener page 26 651 page left column 1004 right to 1005 left 10 binder page 26 same as above 1003 right to 1004 right 11 plasticizer, lubricant page 27 650 page right column 1006 left to 1006 right 12 coating aid, pages 26 to 27 same as above 1005 left ~ 1006 left Surface active agent 13 Static page 27 Same as above 1006 right ~ 1007 left Anti-static agent 14 Matting agent 1008 left ~ 1009 left Also, to prevent deterioration of photographic performance due to formaldehyde gas. For this purpose, it is preferable to add a compound which can react with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503 and can be fixed to the photosensitive material.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

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

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol type and naphthol type couplers. US Pat.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

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

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

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and the same No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, U.S. Pat. Nos. 4,248,962 and 4,782,012.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , RD. No. 1
Bleaching accelerator releasing couplers described in US Pat. Nos. 4,5, 1449, 24241, and JP-A-61-201247.
55,477 and the like, ligand releasing couplers, couplers releasing a leuco dye described in JP-A-63-75747, and couplers releasing a fluorescent dye described in US Pat. No. 4,774,181. To be

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-tert-amylphenyl)
Phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate); benzoic acid esters (for example, 2-ethylhexylbenzoate) , Dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate); amides (eg, N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (for example, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (for example, bis ( 2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-).
5-tert-octylaniline); and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C. or more, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or less can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-1257.
No. 272248 and JP-A No. 1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2 −
It is preferable to add various preservatives or antifungal agents such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers can be mentioned as typical examples. The present invention can be particularly preferably used for a color duplication film.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. Here, the film thickness means a film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days). Further, the film swelling speed T _1/2 can be measured according to a method known in the art, for example, by Photographic Science and Engineering (Photogr.) By A. Green et al.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129, using a serometer (swelling meter). In addition, T _1/2 is 30 in the color developing solution.
℃, the maximum swelling film thickness of 9 reached when treated for 3 minutes 15 seconds
0% is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling rate T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer contains, for example, the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. Is preferred. The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-
Sulfates of amino-N-ethyl-N-β-hydroxyethylaniline are preferred. These compounds are used depending on the purpose.
More than one species may be used in combination.

The color developing solution contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal process is carried out, the black and white development is usually carried out before the color development. The black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-
Known black and white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. The p of these color developing solutions and black-and-white developing solutions
H is generally 9 to 12. Further, the replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per square meter of the light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution. It can also be: When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the processing liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0.1. It is 001-0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. And a slit developing method described in JP-A-63-216050. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fix baths, fixing before bleach-fix processing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids (particularly, sodium persulfate is suitable for color negative films for movies), quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Can be used. Of these, iron (III) aminopolycarboxylate complexes, including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminoboric acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specification: U.S. Pat. No. 3,893,858;
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-51-140129; thiazolidine derivatives described in JP-A-51-140129; JP-B-45-8506;
Nos. 832 and 53-32735, U.S. Pat.
No. 6,561, the thiourea derivative described in West German Patent 1,
127,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,741
8,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40943 and JP-A-49-59644;
Nos. 53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
58, West German Patent 1,290,812, JP-A-53
Compounds described in -95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate and, for example, thiocyanate,
A combination use of a thioether compound and thiourea is also preferable. Examples of the preservatives of the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and European Patent No. 2
Sulfinic acid compounds described in No. 94,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methyl. It is preferable to add 0.1 to 10 mol / liter of an imidazole such as imidazole.

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

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on an emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to improve the effect. Furthermore, a method of further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, and the circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement in the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect by the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Unexamined Patent Publication No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of water to be washed in the water washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use,
Further, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to a replenishment method such as countercurrent or forward flow, and other various conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is shown in Journal of
the Society of Motion Pi
cure and Television Engi
neers, vol. 64, p. 248-253 (1955
May issue).

According to the multistage countercurrent method described in the above document,
Although the amount of washing water can be greatly reduced, there is a problem that bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Also, chlorinated fungicides such as, for example, isothiazolone compounds, thiabendazoles, chlorinated sodium isocyanurate, and others, for example, Horiguchi such as benzotriazole, described in JP-A-57-8542. Hiroshi, "The Chemistry of Bactericidal and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association A fungicide described in "Encyclopedia of Fungicides" (1986) can also be used.

P of washing water in processing the light-sensitive material of the present invention
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and use of the photosensitive material, but are generally at 15 to 45 ° C. for 20 seconds to 1 hour.
A range of 0 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used.

In addition, subsequent to the water washing treatment, a stabilizing treatment may be performed in some cases. An example thereof is a stabilizing bath containing a dye stabilizing agent and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

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

For example, in processing using an automatic processor,
When each of the above-mentioned treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. In order to incorporate them, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, for example, U.S. Pat. No. 3,342,599, Research Disclosure No. 14, 850 and the same No.
Nos. 15, 15 and 159; 1
Aldole compounds described in U.S. Pat.
No. 719,492, a metal salt complex disclosed in JP-A-53-1
The urethane compounds described in JP-A-35628 can be exemplified.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention comprises
U.S. Pat. No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-2380.
No. 56, EP 210,660 A2 and the like.

[0151]

【Example】

Example 1 Emulsions 1-1 to 1-9 were prepared and chemically sensitized to prepare Emulsions 1-A to 1-R as follows.

Preparation of Emulsion 1-1 to Emulsion 1-4 Emulsion 1-1 An aqueous solution prepared by dissolving 9.2 g of gelatin 1, 5.3 g of potassium bromide and 1 liter of distilled water was stirred at 60 ° C.
An aqueous solution of silver nitrate (containing 9.7 g of AgNO ₃ ) and an aqueous solution of KBr (containing 7.0 g of KBr) were added for nucleation, then 38 g of gelatin 2 was added, and the temperature was adjusted to 7
After raising the temperature to 5 ° C. and aging, the pAg was adjusted to 8.0. After adding 0.1 mol of ammonia, aging for 10 minutes,
Neutralized with 1N KNO ₃ . Then, the silver nitrate aqueous solution (A
gNO ₃ (containing 52 g) and an aqueous KBr solution were added at a pAg of 8.5 and an addition rate close to the critical growth rate. Further, an aqueous silver nitrate solution (containing 52 g of AgNO ₃ ) and an aqueous potassium halide solution (an aqueous solution of KBr containing KI) were simultaneously added to prepare tabular core particles. Temperature is 55 ℃
And then potassium iodide aqueous solution (KI 5.3 g
Included) was added. Subsequently, the remaining silver nitrate aqueous solution and potassium bromide aqueous solution are added at a rate of addition close to the critical growth rate by adjusting the pAg to 9.4 to coat the core and form a core / shell type silver iodobromide plate. Particles were prepared. After that, the temperature was lowered to 35 ° C. and washed with water by a usual flocculation method, 78 g of gelatin 2 was added and the pH was adjusted to 6.5 with pAg.
Was adjusted to 8.8 to prepare Emulsion 1-1. The obtained emulsion was grains having an average equivalent circle diameter of 1.0 μm, an average silver iodide content of 9 mol% silver iodide / mol Ag, and an average aspect ratio of 4.3.

Emulsion 1-2 Emulsion 1-in the same manner as Emulsion 1-1 except that the gelatin added after nucleation was changed from gelatin 2 to gelatin 3.
I made 2. The gelatin added after dispersion was gelatin 2. At this time, pAg during growth immediately after ripening was adjusted so that the average aspect ratio was the same as that of emulsion 1-1.

Emulsion 1-3 Emulsion 1-in the same manner as emulsion 1-1 except that the gelatin added after nucleation was changed from gelatin 2 to gelatin 4.
I made 3. The gelatin added after dispersion was gelatin 2. At this time, pAg during growth immediately after ripening was adjusted so that the average aspect ratio was the same as that of emulsion 1-1.

Emulsion 1-4 In Emulsion 1-1, the gelatin added after nucleation was gelatin 2, and after the grain formation, an aqueous solution of gelatin 4 (containing 45 g of gelatin) was added, followed by washing with water and dispersion. Emulsion 1-4 was prepared in the same manner as Emulsion 1-1 except for the above.

Here, gelatin 1 has a weight average molecular weight of about 1.
50,000 represents deionized alkali-treated gelatin, gelatin 2 represents deionized alkali-treated gelatin having an average molecular weight of about 100,000, and gelatin 3 contained 40% of gelatin 2 (ratio of --NH ₂ groups in chemically modified gelatin). ) Shows gelatin which has been phthalated at the phthalation rate shown in FIG. Also gelatin 4
Represents gelatin obtained by phthalating Gelatin 2 with a phthalation rate of 97%.

Gelatin 3 and 4 are 10% by weight of gelatin 2.
40 ° C to 50 ° C, p with respect to the contained gelatin aqueous solution
It was adjusted by phthalating the --NH ₂ group in gelatin 2 by adding phthalic anhydride and reacting with gelatin 2 under the condition of H9.0. By adjusting the conditions such as the amount of phthalic anhydride added, the temperature, and the treatment time, -N
The rate at which the H ₂ groups were phthalated was varied.

Preparation of Emulsion 1-A to Emulsion 1-I Preparation of Emulsion 1-A Emulsion 1-1 was heated to 64 ° C. and sensitizing dye ExS-shown below.
1 is 2.4 × 10 −4 mol / mol Ag, ExS-2 is 1.0 × 10 ⁻⁵ mol / mol Ag, ExS-3 is 3.5 ×.
10 ^-4 mol / mol Ag, chloroauric acid 2.0 × 10 ^-6 mol /
Molar Ag, potassium thiocyanate 2.0 × 10 ^-3 mol /
Optimal chemical sensitization was performed by adding mol Ag and sodium thiosulfate. The amount of sodium thiosulfate was determined so that the sensitivity / fog ratio when exposed for 1/100 second was optimal. Preparation of Emulsion 1-B The obtained emulsion 1-1 was heated to 64 ° C., and the sensitizing dye ExS-1 described later was added to 2.4 × 10 ⁻⁴ mol / mol Ag, ExS−.
2 was 1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 was 3.
5 × 10 ⁻⁴ mol / mol Ag, N, N-dimethylselenourea, chloroauric acid 2.0 × 10 ⁻⁶ mol / mol Ag, sodium thiosulfate 8.0 × 10 ⁻⁶ mol / mol Ag, thiocyanic acid Potassium 2.0 × 10 ⁻³ mol / mol Ag was added, and each was optimally chemically sensitized. The amount of NN dimethylselenourea was determined to optimize the sensitivity / fog ratio. Preparation of Emulsion 1-C Using the obtained Emulsion 1-1, chemical sensitization was performed in the same manner as Emulsion 1-B. However, the selenium compound represented by Se-6 was used instead of NN dimethylselenourea. Preparation of Emulsion 1-D The obtained emulsion 1-2 was optimally chemically sensitized in the same manner as the emulsion 1-B. Preparation of Emulsion 1-E The emulsions 1-3 obtained were optimally chemically sensitized in the same manner as the emulsion 1-B. Preparation of Emulsions 1-F, 1-G and 1-H The resulting emulsion 1-3 was heated to 64 ° C. and the sensitizing dye ExS-1 described below was added at 2.4 × 10 ⁻⁴ mol / mol Ag. , ExS-
2 was 1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 was 3.
5 × 10 ^-4 mol / mol Ag, sodium thiosulfate, selenium compounds, sodium thiosulfate 8.0 × 10 ^-6, chloroauric acid 2.0 × 10 ^-6 mol / mol Ag, potassium thiocyanate 2.0 × Optimum chemical sensitization was carried out by adding 10 ⁻³ mol / mol Ag. The amount of selenium compound was determined to optimize the sensitivity / fog ratio. As the selenium compound, the selenium compounds shown in Se-85, Se-6, and Se-39 were used. Preparation of Emulsion 1-I The emulsions 1-4 obtained were optimally chemically sensitized in the same manner as the emulsion 1-B.

Preparation of seed crystal 1 and seed crystal 2 Preparation of seed crystal 1 A solution containing gelatin 1 (1.5 liters of H ₂ O, 0.75 g of gelatin 1 and 0.7 g of KBr) in a reaction vessel was added 3 times.
Keeping the temperature at 5 ° C and stirring the AgNO ₃ aqueous solution (AgNO _3
3 containing 0.85g) and halogen aqueous solution (KBr0.5
(Including 9 g) was simultaneously added by the double jet method with rapid stirring to form nuclei. After the temperature was raised to 60 ° C. and ripening was performed, an aqueous solution containing gelatin 2 (0.07 liter of water, containing 8.3 g of gelatin 2) was added. After the AgNO ₃ aqueous solution (containing AgNO ₃ 227.1 g) and the KBr aqueous solution were simultaneously added by the double jet method near the critical growth rate while keeping pAg constant, 35
After cooling down to ℃, wash with water by the usual flocculation method,
50 g of gelatin 2 was added to adjust pH to 5.8 and pAg to 8.8. The resulting seed crystal grains were tabular grains having an average equivalent circle diameter of 0.71 μm and an average aspect ratio of 8.8. Preparation of seed crystal 2 Gelatin 1 to gelatin 5 added to the reaction vessel
Seed crystal 2 was prepared in the same manner as seed crystal 1 except that the gelatin added after ripening was changed from gelatin 2 to gelatin 4. At this time, pAg at the time of growth immediately after aging was adjusted so that the equivalent circle diameter and the average aspect ratio were the same as those of the seed crystal 1.

Here, gelatin 5 represents gelatin obtained by phthalating gelatin 1 with a phthalation ratio of 98%. Here, gelatin 5 was prepared by following the method of preparing gelatin 2 to gelatin 3 and 4.

Preparation of Emulsion 1-5 to Emulsion 1-9 Preparation of Emulsion 1-5 Seed crystal 1 above was added to AgNO_ThreeThe amount of 0.134 mol is
Weigh out 1.2 liters of water and 38 g of gelatin 2
And KBr are added and the mixture is kept at 75 ° C., then an aqueous silver nitrate solution (Ag
NO_Three43.9 g) and KBr aqueous solution with pAg
While keeping constant, double jet at the same time
Stirred well. AgNO3 aqueous solution (AgNO _Three43.5 g
(Including) and a KBr aqueous solution were added by the double jet method.
After the above formation, a silver nitrate aqueous solution (AgNO_ThreeContains 42.6 g
Water) and an aqueous halogen solution (KBr water solution containing 28% KI)
Liquid) was added while accelerating the flow rate. Further benzene thios
Rufonic acid was added and the silver potential was adjusted to -80 m with an aqueous KBr solution.
Adjusted to V. Fine silver iodide with an average equivalent circle diameter of 0.025 μm
Gradually add 8.5 g of silver emulsion within 5 seconds in terms of silver nitrate
Then, after 30 seconds, the silver nitrate aqueous solution was added while decelerating the flow rate.
Was. A potassium iridium hexachloride solution was added on the way.
After this, the temperature is lowered to 35 ° C. and the usual flocculation method is applied.
Wash with water, add 80 g of gelatin 2 and adjust the pH to 6.5.
Ag was adjusted to 8.8 to prepare Emulsion 1-5. Got
The emulsion had an average equivalent circle diameter of 1.4 μm and an average aspect ratio of 8.
It was an emulsion of 8. Preparation of emulsion 1-6 Same as emulsion 1-5 except that seed crystal 1 was changed to seed crystal 2.
Emulsions 1-6 were prepared. But adjust the pAg of growth
The average aspect ratio of the obtained silver halide grains is 1-5.
Combined with. Preparation of Emulsion 1-7 Gelatin to be weighed at the same time as seed crystals is gelatin from gelatin 2.
Emulsion 1-7 was prepared in the same manner as Emulsion 6 except that it was changed to 4.
did. However, halogen obtained by adjusting the pAg of growth
The average aspect ratio of silver halide grains was adjusted to Emulsion 1-5. Preparation of Emulsion 1-8 The seed crystal 1 was added to AgNO_ThreeThe amount of 0.134 mol is
Weigh out 1.2 liters of water and 38 g of gelatin 2
And KBr were added, the temperature was kept at 75 ° C, and thiourea dioxide was added.
After that, an aqueous solution of silver nitrate (AgNO_ThreeIncluding 43.9 g) and
Double jet the KBr aqueous solution while keeping the pAg constant.
The mixture was stirred vigorously while being added simultaneously. Below is emulsion 1
It adjusted like 5th. Preparation of Emulsion 1-9 Seed crystal 2 above was added to AgNO_ThreeThe amount of 0.134 mol is
Weigh out 1.2 liters of water and 38 g of gelatin 4.
And KBr were added, the temperature was kept at 75 ° C, and thiourea dioxide was added.
After that, an aqueous solution of silver nitrate (AgNO_ThreeIncluding 43.9 g) and
Double jet the KBr aqueous solution while keeping the pAg constant.
The mixture was stirred vigorously while being added simultaneously. Below is emulsion 1
It adjusted like 5th. However, it is obtained by adjusting the pAg of growth
The average aspect ratio of the obtained silver halide grains to emulsion 1-
Adjusted to 5.

Preparation of Emulsion 1-J to Emulsion 1-R Preparation of Emulsion 1-J The resulting emulsion 1-5 was heated to 64 ° C. and the sensitizing dye ExS-1 described later was added at 4.3 × 10 4. ^-4 mol / mol Ag, ExS-
2. 1.8 × 10 ⁻⁵ mol / mol Ag, ExS-3 6.
Optimal by adding 3 × 10 ⁻⁴ mol / mol Ag, sodium thiosulfate, 3.5 × 10 ⁻⁶ mol / mol Ag chloroauric acid, and 3.5 × 10 ⁻³ mol / mol Ag potassium thiocyanate Was chemically sensitized. The amount of sodium thiosulfate is sensitivity /
It was decided that the fogging ratio would be optimum. Preparation of Emulsion 1-K The resulting Emulsion 1-5 was heated to 64 ° C. and the sensitizing dye ExS-1 described later was added at 4.3 × 10 ⁻⁴ mol / mol Ag, ExS-.
2. 1.8 × 10 ⁻⁵ mol / mol Ag, ExS-3 6.
3 × 10 ⁻⁴ mol / mol Ag, sodium thiosulfate 2.5
^{X10 -6} mol / mol Ag, chloroauric acid 3.5 × 10 ^-6 mol / mol Ag, and potassium thiocyanate 3.5 × 10 ^-3 mol / mol Ag were added to each to achieve optimum chemical sensitization. Was applied. The amount of N, N-dimethylselenourea was determined to optimize the sensitivity / fog ratio. Preparation of Emulsion 1-L The obtained emulsion 1-5 was subjected to the same chemical sensitization as for 1-K. However, the compound represented by Se-6 shown in Chemical formula 7 was added instead of N—N dimethylselenourea. Preparation of Emulsion 1-M The obtained emulsion 1-6 was subjected to the same chemical sensitization as for 1-K. Preparation of Emulsion 1-N The obtained emulsion 1-6 was subjected to the same chemical sensitization as for 1-L. Preparation of Emulsion 1-O The obtained emulsion 1-7 was subjected to the same chemical sensitization as for 1-K. Preparation of Emulsion 1-P The obtained emulsion 1-7 was subjected to the same chemical sensitization as for 1-L. Preparation of Emulsion 1-Q The obtained emulsion 1-8 was subjected to the same chemical sensitization as for 1-L. Preparation of Emulsion 1-R The obtained emulsion 1-9 was subjected to the same chemical sensitization as for 1-L.

Preparation and Evaluation of Coating Samples Emulsions 1-A to R and a protective layer were coated on a triacetate cellulose film support provided with an undercoat layer at the coating amounts shown below, respectively. Application samples 1-A to R were prepared. Emulsion coating conditions (1) Emulsion layer ・ Emulsion ... Various emulsions (silver 2.1 × 10 ^-2 mol / m ² ) -Coupler shown in the following "Chemical formula 26" (1.5 × 10 ^-3 mol / m ² ).

[0164]

Embedded image

Tricresyl phosphate (1.10 g / m ² ), gelatin (2.30 g / m ² ) (2) protective layer, 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0 .08g / m ²⁾ · gelatin (1.80g / m ²⁾ these samples 40 ° C., the relative humidity of 70% 14
After standing for a period of time, it was exposed for 1/100 seconds through a SC-50 filter manufactured by Fuji Photo Film and a continuous wedge, and the color development described below was performed.

[0166] Negative Processor FP-350 manufactured by Fuji Photo Film Co., Ltd. was used and processed in the following manner (until the cumulative replenishment amount of the solution became 3 times the capacity of the mother liquor tank). (Processing method) Process processing time Processing temperature Replenishment amount Color development 2 minutes 45 seconds 38 ° C. 45 ml Bleach 1 minute 00 seconds 38 ° C. 20 ml Bleaching solution overflows into bleach-fixing tank 3 minutes 15 seconds 38 ° C. 30 ml Washing with water (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Washing with water (2) 1 minute 00 seconds 35 ° C 30 ml Stability 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ℃ * Replenishment amount is 35 mm width 1.1 m per length (equivalent to 24 Ex. 1) Next, the composition of the treatment liquid is described. (Color developer) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.10 (bleaching solution) Common for tank solution and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH _{3) 2 N-CH 2 -CH} 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 milliliter PH 1.0 (adjusted with ammonia water and nitric acid) by adding water 6.3 (bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 ml 400.0 ml Ammonia water (27%) 6.0 ml-1.0 liter 1.0 liter by adding water pH (adjusted with ammonia water and acetic acid) 7.2 7.3 (Wash solution ) Common to tank liquid and replenisher A mixed bed type in which tap water is filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Pass the water through the column to adjust the concentration of calcium and magnesium ions to 3 mg / Liter or less. Subsequently, the addition of sodium isocyanurate dichloride 20mg / liter and sodium 0.15 g / l of sulfuric acid. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizer) Tank liquid and replenisher are common (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 The concentration of each sample was measured with a green filter to measure fog and sensitivity. I asked. For the sensitivity, the reciprocal of the exposure amount that gives a density of 0.2 on the fog was obtained, and the sensitivity of 1-A from coating sample 1-A to coating sample 1-J was set to 100, and the relative values are shown in Table 1. Sample 1-K to coated sample 1
Up to -R, the sensitivity of the coated sample 1-K was set to 100 and shown in Table 2 as relative values.

[0167]

[Table 1]

[0168]

[Table 2]

In contrast to 1-A in Table 1, even when unmodified gelatin such as 1-B or 1-C is used, the effect of high sensitivity is obtained when selenium sensitization is used, but fog And the degree of sensitization is insufficient. Further, 1-C has low fog as compared with 1-B.
Although there is the effect shown in, the fog and sensitivity are still not sufficient. On the other hand, it can be seen that a surprising effect can be seen by further selenium sensitization using modified gelatin as in 1-D of the present invention. Further, from the result of 1-I, the effect of the present invention was hardly found in the method of using the modified gelatin which is conventionally known in the case of washing with water. Further, when the compounds represented by 1-F, 1-G and 1-H were used, the effect was larger than expected when an emulsion using modified gelatin was used, and a surprising effect was obtained. This effect was also observed in the case of seed crystals using modified gelatin as shown in Table 2 and in the case of reduction sensitization.

Example 2 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.326 (Ciba
2 parts by weight of Ciba-Geigy) and then 3
After melting at 00 ° C, it was extruded from a T-die, longitudinally stretched 3.3 times at 140 ° C, then laterally stretched 3.3 times at 130 ° C, and heat set at 250 ° C for 6 seconds. To obtain a PEN film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: I-1, described in Japanese Patent Publication No. 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV irradiation treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² ,
_{(CH 2 = CHSO 2 CH 2} CH 2 NHCO) 2 CH 2 0.012g / m 2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, using a bar coater ), An undercoat layer was provided on the high-temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 1
15 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm (secondary agglomerated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
g / m ^2, it was coated with poly (polymerization degree 10) oxyethylene -p- nonylphenol 0.005 g / m ^2, and resorcin. 3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.
14 μm, single axis 0.03 μm, saturation magnetization 89 emu / g,
Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which has been treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06 g / m ²
1.2 g / m ^{2 of} diacetyl cellulose (iron oxide was dispersed in an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃₀ as a curing agent. 3 g / m ²
Coating with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a film thickness of 1.2 μm.
To obtain a magnetic recording layer of Silica particles (0.
3 μm) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) treated and coated with aluminum oxide (0.15 μm) as an abrasive to be 10 mg / m ² respectively. did. 115 for drying
It was carried out at 6 ° C. for 6 minutes (115 ° C. for all the rollers and conveyance devices in the drying zone). The color density increase of D ^B of the magnetic recording layer by X-light (blue filter) was about 0.1, the saturation magnetization moment of the magnetic recording layer was 4.2 emu / g, and the coercive force was 7.3 × 10 ^4. The A / m and the squareness ratio were 65%.

3-3) Preparation of sliding layer Diacetylcellulose (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 ) mixture was applied. This mixture was melted at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1), poured and dispersed in propylene glycol monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone. (Average particle size: 0.01 μm). 15 mg / m of silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight of aluminum oxide (0.15 μm) coated as an abrasive) ^It was added so that it would be ^2. Drying was carried out at 115 ° C. for 6 minutes (all the rollers and the conveying device in the drying zone were 115 ° C.) The sliding layer had a dynamic friction coefficient of 0.06 (5 mmφ stainless hard balls, a load of 100).
g, speed 6 cm / min), coefficient of static friction 0.07 (clip method), and coefficient of dynamic friction between the emulsion surface and the sliding layer described later was 0.12.

4) Coating of Photosensitive Layer Next, each layer having the following composition was multilayer coated on the side opposite to the back layer obtained above, and the sixth layer was prepared with emulsions 1-A to 1-A prepared in Example 1. 1-I and 1-J to I-R were added and color negative films were applied, and samples 2-A to 2-I and 2-J were applied.
~ 2-R was created.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (first antihalation layer) black colloidal silver 0.08 gelatin 0.70 Second layer (second antihalation layer) black colloidal silver 0.09 gelatin 1.00 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.70

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.20 Silver iodobromide Emulsion B Silver 0.33 ExS-1 3.8 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.2 × 10 ^-4 ExC-1 0.17 ExC-2 0.02 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10

Fifth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion C Silver 0.15 Silver iodobromide emulsion D Silver 0.46 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.14 ExC-2 0.02 ExC-3 0.03 ExC-4 0.090 ExC-5 0.02 ExC-6 0.01 Cpd-4 0.030 Cpd-2 0.05 HBS-1 0.10 Gelatin 0.75

Sixth layer (high-sensitivity red-sensitive emulsion layer) Emulsion prepared in Example 1 Silver 1.30 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 × 10 ^-5 ExS-3 3.6 × 10 ^-4 ExC-1 0.12 ExC-3 0.11 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 Cpd-4 0.020 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40

Seventh layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 Polyethyl acrylate latex 0.15 Gelatin 1.10

Eighth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion F Silver 0.57 ExS-7 6.2 × 10 ^-4 ExS-8 1.4 × 10 ^-4 ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-5 ExS-6 2.7 × 10 ^-4 ExM-3 0.410 ExM-4 0.086 ExY-1 0.070 ExY-5 0.0070 HBS-1 0.30 HBS-3 0.015 Cpd-4 0.010 Gelatin 0.95

Ninth layer (medium-speed green emulsion layer) Silver iodobromide emulsion G Silver 0.48 Silver iodobromide emulsion H Silver 0.48 ExS-4 4.8 × 10 ^-5 ExS-7 9.3 × 10 ^-4 ExS-8 2.1 × 10 ^-4 ExC-8 0.0020 ExM-3 0.115 ExM-4 0.035 ExY-1 0.010 ExY-4 0.010 ExY-5 0.0050 Cpd-4 0.011 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 Gelatin 0.80

The 10th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.30 ExS-4 4.5 × 10 ^-5 ExS-7 5.3 × 10 ^-4 ExS-8 1.2 × 10 ^-4 ExC-1 0.021 ExM-1 0.010 ExM-2 0.030 ExM-5 0.0070 ExM-6 0.0050 Cpd-3 0.017 Cpd-4 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Eleventh layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.10 Silver iodobromide emulsion L Silver 0.25 ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.75 ExY-3 0.40 ExY-4 0.040 Cpd-2 0.10 Cpd-4 0.01 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 2.10

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion M Silver 0.58 ExS-9 3.5 × 10 ^-4 ExY-2 0.070 ExY-3 0.070 ExY-4 0.0050 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 Cpd-4 0.02 HBS-1 0.075 Gelatin 0.55

Fourteenth layer (first protective layer) Silver iodobromide emulsion N silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.06 B-2 (diameter 1.7 μm) 0.09 B-3 0.13 ES-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-18, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0191]

[Table 3]

In Table 3, (1) Emulsions J to M were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions C to D, G to I, and M were subjected to gold sensitization and sulfur sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples in JP-A-3-237450. And selenium sensitization. (3) When a high voltage electron microscope is used for the tabular grains, dislocation lines as described in JP-A-3-237450 are observed. (4) Emulsions A to D, G, H and J to M are Rh, Ir and F
e in an optimal amount. The tabularity is defined as Dc / t ² where Dc is the average equivalent circle diameter in the projected area of the tabular grains and t is the average thickness of the tabular grains.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethaneethanesulfonate and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) and 0.5 g were put into a 700 ml pot mill, and dye ExF- 5.0 g of 2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

[0195]

Embedded image

[0196]

Embedded image

[0197]

Embedded image

[0198]

Embedded image

[0199]

Embedded image

[0200]

Embedded image

[0201]

Embedded image

[0202]

Embedded image

[0203]

Embedded image

[0204]

Embedded image

[0205]

Embedded image

[0206]

Embedded image

[0207]

Embedded image

[0208]

Embedded image

[0209]

Embedded image

[0210]

Embedded image

[0211]

Embedded image

Each of the obtained samples was allowed to stand for 14 hours under the conditions of 40 ° C. and 70% relative humidity and then passed through a continuous wedge to 1 /
After exposure for 100 seconds, the same treatment as in Example 1 was performed. However, the color development time was 3 minutes and 15 seconds. The density of each of the obtained samples was measured with a red filter, and the same treatment as in Example 1 was performed to obtain the fog and the sensitivity. For the sensitivity, the reciprocal of the exposure amount that gives a density of 0.2 on the fog was obtained, and the coated sample 2
From -A to coating sample 2-J, the sensitivity of 1-A is set to 100, and the relative values are shown in Table 4. From coating sample 2-K to coating sample 2-R, the sensitivity of coating sample 2-K is 100.
Are shown in Table 5 as relative values.

[0213]

[Table 4]

[0214]

[Table 5]

As is clear from Tables 4 and 5, the emulsion of the present invention has a clearly increased sensitivity fog ratio even when coated in multiple layers.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 18, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

[0007]

The object of the present invention is as follows.
(1) a silver halide emulsion formed in a dispersion medium solution
And the dispersion medium --NH _Two Percentage of chemically modified groups
Contains gelatin, characterized in that it is 30% or more
Nucleation or ripening of the silver halide grains in a dispersion medium or
Growth is carried out and the silver halide emulsion is at least
Characterized by chemical sensitization, including lens sensitization
Halogen silver emulsion. (2) -NH in the dispersion medium_Two Percentage of chemically modified groups
Of 30% or more in a dispersion medium
Nucleation, ripening or growth of silver halide grains
The silver halide grains obtained by
Chemical sensitization including selenium sensitization
A silver halide photographic emulsion characterized in that (3) A selenium sensitizer represented by the following general formula (I) is selected.
(1) or (2) characterized by being sensitized
Silver halide emulsion of the general formula (I)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Preparation of Emulsion 1-A to Emulsion 1-I Preparation of Emulsion 1-A Emulsion 1-1 was heated to 64 ° C. and sensitizing dye ExS-shown below.
1 is 2.4 × 10 −4 mol / mol Ag, ExS-2 is 1.0 × 10 ⁻⁵ mol / mol Ag, ExS-3 is 3.5 ×.
10 ^-4 mol / mol Ag, chloroauric acid 2.0 × 10 ^-6 mol /
Molar Ag, potassium thiocyanate 2.0 × 10 ^-3 mol /
Optimal chemical sensitization was performed by adding mol Ag and sodium thiosulfate. The amount of sodium thiosulfate was determined so that the sensitivity / fog ratio when exposed for 1/100 second was optimal. Preparation of Emulsion 1-B The obtained emulsion 1-1 was heated to 64 ° C., and the sensitizing dye ExS-1 described later was added to 2.4 × 10 ⁻⁴ mol / mol Ag, ExS−.
2 was 1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 was 3.
5 × 10 ⁻⁴ mol / mol Ag, N, N-dimethylselenourea, chloroauric acid 2.0 × 10 ⁻⁶ mol / mol Ag, sodium thiosulfate 8.0 × 10 ⁻⁶ mol / mol Ag, thiocyanic acid Potassium 2.0 × 10 ⁻³ mol / mol Ag was added, and each was optimally chemically sensitized. The amount of NN dimethylselenourea was determined to optimize the sensitivity / fog ratio. Preparation of Emulsion 1-C Using the obtained Emulsion 1-1, chemical sensitization was performed in the same manner as Emulsion 1-B. However, the selenium compound represented by Se-6 was used instead of NN dimethylselenourea. Preparation of Emulsion 1-D The obtained emulsion 1-2 was optimally chemically sensitized in the same manner as the emulsion 1-B. Preparation of Emulsion 1-E The emulsions 1-3 obtained were optimally chemically sensitized in the same manner as the emulsion 1-B. Preparation of Emulsions 1-F, 1-G and 1-H The resulting emulsion 1-3 was heated to 64 ° C. and the sensitizing dye ExS-1 described below was added at 2.4 × 10 ⁻⁴ mol / mol Ag. , ExS-
2 was 1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 was 3.
5 × 10 ^-4 mol / mol Ag, sodium thiosulfate, selenium compounds, sodium thiosulfate 8.0 × 10 ^-6, chloroauric acid 2.0 × 10 ^-6 mol / mol Ag, potassium thiocyanate 2.0 × Optimum chemical sensitization was carried out by adding 10 ⁻³ mol / mol Ag. The amount of selenium compound was determined to optimize the sensitivity / fog ratio. As the selenium compound, the selenium compounds shown in Se-85, Se-39, and Se-6 were used. Preparation of Emulsion 1-I The emulsions 1-4 obtained were optimally chemically sensitized in the same manner as the emulsion 1-B.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03C 7/00 520 G03C 7/00 520 530 530

Claims (5)

[Claims] 1. A silver halide emulsion formed in a dispersion medium solution, wherein the halogen is contained in a dispersion medium containing gelatin in which the number of chemically modified --NH ₂ groups in the dispersion medium is 30% or more. A silver halide emulsion characterized in that the silver halide grains are nucleated, ripened or grown, and the silver halide emulsion is subjected to chemical sensitization including at least selenium sensitization. 2. A seed formed by nucleation, ripening or growing of silver halide grains in a dispersion medium, characterized in that the proportion of the number of chemically modified --NH ₂ groups in the dispersion medium is 30% or more. A silver halide photographic emulsion, characterized in that the photographic emulsion containing silver halide grains obtained by growing using a crystal has been chemically sensitized including selenium sensitization. 3. The silver halide emulsion according to claim 1, which is selenium sensitized with a selenium sensitizer represented by the following general formula (I). General formula (I) In the formula, Z ₁ is a hydrogen atom, an aliphatic hydrocarbon group, an aryl group,
Heterocyclic group, OR ₁ , N (R ₂ ) R ₃ is represented, Z ₂ is an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, R ₁ , R
₂ , R ₃ is a hydrogen atom, an aliphatic hydrocarbon group, an aryl group,
Represents a heterocyclic group. 4. The silver halide emulsion according to claim 1, wherein reduction sensitization is performed in the process of forming silver halide grains. 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material comprising at least one silver halide emulsion according to claim 1 as a light-sensitive silver halide emulsion contained in said silver halide emulsion layer.