JPH0611780A - Silver halide photographic emulsion and photographic sensitive material using same - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic emulsion and the photographic sensitive material especially low. in fog of a blue-sensitive layer and improved in sensitivity and pressure resistance. CONSTITUTION:Silver halide grains are formed while iodide ions are abruptly produced and the silver halide grains are spectrally sensitized with a sensitizing dye represented by formula in which each of Z1 and Z2 is a nonmetallic atomic group necessary to form a 5- or 6-membered heterocycle together with N and C; each of R3 and R4 is alkyl: X1<-> is an anion; and p is 1 or 2.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide photographic emulsion and a photographic light-sensitive material containing this emulsion.

More specifically, the present invention relates to a silver halide photographic emulsion having a particularly low fog in the blue-sensitive layer and having improved sensitivity and pressure resistance, and a photographic light-sensitive material containing this emulsion.

[0003]

2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more stringent, and in addition to photographic characteristics such as high sensitivity and excellent graininess, higher level requirements have been made for toughness such as pressure. ing.

In order to increase the sensitivity of silver halide grains, it is preferable that the silver iodide (iodide ion) content is uniform in each grain and between grains in terms of uniform chemical sensitization. It is believed that.

JP-A-2-68538 (Japanese Patent Application No. 63-2
No. 20187), in the formation of silver halide grains, by using a halogen ion sustained-release agent or silver halide fine particles as a halogen ion supply source in place of a conventional aqueous solution of a halogen salt, it is possible to prevent the occurrence of halide in and between grains. A technique of eliminating the uniform distribution is disclosed.

However, it is reported that the formation of silver halide grains while rapidly generating iodide ions is important for producing an emulsion having low fog and improved sensitivity and pressure. Not not.

On the other hand, it has been known that the pressure fog is aggravated by adding a sensitizing dye, and research for improving the pressure resistance is ongoing.

JP-A-63-220228 discloses tabular grains having improved pressure resistance.

However, the silver iodide content distribution of the grains obtained by this patent is wide and there is a problem in the uniformity of chemical sensitization.

Further, the pressure resistance is insufficient for use in the blue-sensitive layer located above the silver halide photographic light-sensitive material, and it is necessary to thicken the protective layer.

Therefore, under the present circumstances, the advantage of tabular grains for improving the sharpness of the lower layer has not been fully utilized.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion which has a low fog in the blue-sensitive layer, a high sensitivity and an improved pressure property, and a photographic light-sensitive material containing the same. is there.

[0013]

[Means for Solving the Problems] The above-mentioned object is as follows (1)
It was solved by means of (7).

That is, (1) silver halide grains are formed while rapidly generating iodide ions, and the silver halide grains are spectrally analyzed by a sensitizing dye represented by the formula (I) shown in the chemical formula 3 below. A silver halide photographic emulsion characterized by being sensitized.

[0015]

[Chemical 3] In formula (I), Z ₁ and Z ₂ together with N and C are 5 to 6
Represents a non-metal atom group forming a member heterocycle, and R ₃ and R
₄ represents an alkyl group, X ₁ ^- represents an anion,
p represents 1 or 2. (2) Ten of iodide ion releasing agents present in the reaction vessel
The silver halide photographic emulsion according to (1) above, wherein 0 to 50% of the iodide ion-releasing agent substantially completes the release of iodide ions within 180 consecutive seconds. (3) The silver halide photographic emulsion according to (1) above, which is a silver halide grain formed by rapidly producing iodide ions using an iodide ion releasing agent and an iodide ion release controlling agent. (4) The reaction that rapidly produces iodide ions is a second-order reaction that is substantially proportional to the iodide ion-releasing agent concentration and the iodide ion-releasing regulator concentration, and its second-order reaction rate constant is 1000 to 5 The silver halide photographic emulsion according to (1) above, which uses an iodide ion-releasing agent having a density of × 10 ^-3 (M ^-1 · sec ^-1 ). (5) The silver halide photographic emulsion as described in (1) above, which rapidly produces iodide ions from the iodide ion-releasing agent represented by the formula (II) shown below.

[0016]

[Chemical 4] In formula (II), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. (6) A silver halide tabular grain having an aspect ratio of 2 to 30 is 100 times the projected area of all silver halide grains in the emulsion.
The silver halide photographic emulsion described in (1) above, which accounts for 50 to 50%. (7) A photographic light-sensitive material containing the silver halide photographic emulsion according to any one of (1) to (6) above.

The present invention will be described in more detail below.

First, the spectral sensitizing dye represented by the following formula (I) will be described in detail.

[0019]

[Chemical 5] R ₃ and R ₄ are alkyl groups. Examples of the alkyl group represented by R ₃ and R ₄ include, for example, 1 to 1 carbon atoms.
8, preferably 1-7, particularly preferably 1-4 alkyl groups {eg unsubstituted alkyl groups (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Hexyl, octyl, dodecyl, octasil), substituted alkyl groups such as aralkyl groups (eg benzyl,
2-phenylethyl), hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl Group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl, 2- (3-sulfopropoxy) ethyl,
2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine-2) -On-1-yl) ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl,
2-methanesulfonylaminoethyl, allyl group}.

The alkyl group of at least one of R ₃ and R ₄ has at least one carbon atom of at least 3
It is preferable that each hydrogen atom is bonded to an atom that is not a hydrogen atom. R ₃ and R ₄ are alkyl groups having an organic acid group and are represented by the formula (III) shown below.

[0021]

[Chemical 6] In formula (III), A has an organic acid group. k and o each represent an integer of 0 to 5. Examples of the organic acid group include a carboxy group, a sulfo group and a phosphoryl group.

At least one carbon atom is at least 3
Particularly detailed examples of the alkyl group bonded to atoms that are not hydrogen atoms will be given.

For example, 2-methylpropyl, t-butyl, 2-methylbutyl, 1,1-dimethylpropyne, 3
-Methylbutyl, 1,2-dimethylpropyl, 2-methylpentyl, 1,1-dimethylbutyl, 1-isopropylpropyl, 3-methylpentyl, 1,2-dimethylbutyl, 1-ethyl-methylpropyl, 4-methylpentyl , 1,3-dimethylbutyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1,4-dimethylpentyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 2-methylhexyl, 1-methyl- 4,4
-Dimethylpentyl, 3,4,4-trimethylpentyl, 3,5,5-trimethylhexyl, 3-carboxy-1-methylpropyl, 3-carboxybutyl, 3-carboxy-1-methylbutyl, 3-carboxy-1, 1
-Dimethylpropyl, 4-carboxy-3-methylbutyl, 2-carboxy-2-methylpropyl, 3-carboxy-2-methylpropyl, 1-methyl-3-sulfopropyl, 3-sulfobutyl, 1-methyl-3-sulfobutyl , 1,1-dimethyl-3-sulfopropyl, 2-methyl-2-sulfopropyl, 2-methyl-3-sulfopropyl.

Among the formula (III), k = 2,3 and o =
0,1, A = sulfo group is preferable. More preferably k
= 2 and o = 0.

5 to 6 formed by Z ₁ and Z ₂
Examples of the member heterocycle include the following.

For example, a thiazole nucleus (eg, thiazole, 4-methylthiazole, 4-phenylthiazole,
4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4- Methylbenzothiazole, 5-
Methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6
-Methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5
-Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4 -Phenylbenzothiazole, 5-styrylbenzothiazole), naphthothiazole nucleus (eg naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,2].
1-d] thiazole, 8-methoxynaphtho [2,1-
d] thiazole, 5-methoxynaphtho [2,3-d] thiazole), thiazoline nucleus (eg thiazoline, 4-
Methylthiazoline, 4-nitrothiazoline), oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzo Oxazole nucleus (eg, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5
-Bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-
Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4, 6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5 -Nitronaphtho [2,1-d] oxazole), oxazoline nucleus (e.g. 4,4-dimethyloxazoline), selenazole nucleus (e.g. 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzo Renazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6- Nitrobenzoselenazole), a naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole), a tellurazole nucleus (for example, benzoterrazole, 5-methylbenzoterrazole, 5-methoxybenzoterrazole, naphtho [1,2-d] telrazole), 3,3-dialkylindolenine nucleus (eg,
3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,
3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (for example, 1-alkyl imidazole, 1-alkyl-4-phenyl imidazole, 1-alkyl benzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5-
Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho [1,2-d] imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-
5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5
6-dichlorobenzimidazole, 1-aryl-5-
Methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-arylnaphtho [1,2-
d] imidazole}. Here, the above-mentioned alkyl group has 1 to 8 carbon atoms, for example, methyl, ethyl,
Unsubstituted alkyl groups such as propyl, isopropyl and butyl and hydroxyalkyl groups (eg 2-hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are methyl and ethyl. The aforementioned aryl group is
For example, phenyl {eg halogen (eg chloro)
Represents substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, Pyridine nucleus (for example, 2-pyridine, 5-methyl-2-pyridine), quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2) -Quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-
2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, isoquinoline, 6-nitro-1-
Isoquinoline, 3,4-dihydro-1-isoquinoline,
6-nitro-3-isoquinoline), imidazo [4,5-
b] quinoxaline nucleus (eg 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-
Diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,
Mention may be made of pyrimidine nuclei.

X ₁ represents an anion. P represents 1 or 2, and when the spectral sensitizing dye forms an inner salt, P is 1
Represents

Specific examples of the compound of formula (I) of the present invention are shown below.

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9] The compound represented by the formula (I) used in the present invention is a known compound,
It can be easily synthesized.

For example, FM Harm
er) "Heterocyclic compound-Cyanine soybean and related compound-
(Heterocyclic Compound −Cyanine dyes and related
compounds−) ”, John Wiley & Sans, New York, London,
(1964)., DMSturmer
), "Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics in
heterocyclic chemistry-) ", Chapter 18, Section 14,
Pp. 482-515, John Wiley & Sans, New York, London, (1977), Day J. Fly (DJFry)
Author, "Rodd's Chemistry of Carbon Compounds",
(2nd.Ed.vol.IV.part B. 1977), Chapter 15, Chapter 3
69-422: (2nd.Eb.vol.IV.part B.1985), Chapter 15, 267-296, Elsvier Science Publishing Company Inc. Published,
Literature such as New York can be cited.

The spectral sensitizing dye can be added at any time before the coating step. After chemical sensitization, during chemical sensitization,
At the same time as the addition of the chemical sensitizer, before the chemical sensitization, the washing process,
Although any of the grain forming steps may be performed, it is preferable that the chemical sensitization is started after the nucleation of grain formation is completed.

Two or more kinds of spectral sensitizing dyes may be used in combination. In this case, two or more kinds of spectral sensitizing dyes may be mixed and added at the same time, or may be added separately at different times. Further, the spectral sensitizing dye may be added at once, dividedly dividedly added several times, or continuously added using a pump or the like.

Further, the same or different spectral sensitizing dye may be further added at the end of the chemical sensitization or at any time after the end of the chemical sensitization until the coating.

To add the spectral sensitizing dyes used in the present invention to the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or, for example, water, acetone, methanol, ethanol. It may be added to the emulsion by dissolving it in a solvent such as propanol, methyl cellosolve or phenol alone or in a mixed solvent.

If ultrasonic waves can be used for melting, US Pat. No. 3,469,987 and Japanese Patent Publication No. 46-2 are available.
No. 4185, No. 44-23389, No. 44-2755.
5, U.S. Pat. No. 5,722,091, U.S. Pat.
135, 4,006,025, JP-A-53-1.
02733, 58-105141, 51-74.
A method of adding a spectral sensitizing dye by the method described in JP-A No. 624 or the like is also preferable.

The addition amount of the spectral sensitizing dye used in the present invention can be arbitrarily selected, but it is 1 × 10 ^-4 to 1 mol per mol of silver halide.
1 × 10 ⁻² is preferable, and more preferably 4 × 10 ⁻⁴
It is 7 × 10 ⁻³ , and more preferably 7 × 10 ^{−4 to} 5 × 10 ⁻³ .

Next, the compound represented by the formula (II) will be described.

The iodide ion-releasing agent represented by the formula (II) of the present invention is used in order to make the halogen composition uniform within and between the individual silver halide grains in JP-A-2-68538. Partial overlap with the compound used. However, by forming silver halide grains by rapidly forming iodide ions in the presence of the iodide ion-releasing agent represented by the formula (II), fog is low, and sensitivity and pressure property are improved. It was unexpected that the present inventors found out that a silver halide emulsion could be obtained. The iodide ion-releasing agent represented by the following formula (II) represented by Chemical formula 10 of the present invention will be described in detail.

[0041]

[Chemical 10] In formula (II), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. Explaining the compound represented by the formula (II) in more detail, R is, for example, 1 to 30 carbon atoms.
An alkyl group, a C2-C30 alkenyl group, a C2-C3 alkynyl group, a C6-C30 aryl group,
Aralkyl group having 7 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, acyl group having 1 to 30 carbon atoms, carbamoyl group, alkyl or aryloxycarbonyl group having 2 to 30 carbon atoms, and 1 to 30 carbon atoms An alkyl or aryl sulfonyl group and a sulfamoyl group are preferable. R is preferably the above group having 20 or less carbon atoms, and particularly preferably the above group having 12 or less carbon atoms. The number of carbon atoms is preferably within the above range in terms of solubility and addition amount, and R is preferably substituted, and preferable substituents include the following. The substituent may be further substituted with another substituent.

For example, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), an alkenyl group ( For example, allyl, 2-butenyl, 3-pentenyl), alkynyl group (eg, propargyl, 3-pentynyl), aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocycle. A cyclic group (for example, pyridyl, furyl, imidazolyl, piperidyl, morpholyl), an alkoxy group (for example, methoxy, ethoxy, butoxy), an aryloxy group (for example, phenoxy, naphthoxy),
Amino group (eg, unsubstituted amino, dimethylamino, ethylamino, anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, unsubstituted ureido, N-methylureido, N-phenylureido), Urethane group (eg methoxycarbonylamino, phenoxycarbonylamino), sulfonylamino group (eg methylsulfonylamino, phenylsulfonylamino), sulfamoyl group (eg sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl) , Carbamoyl group (eg, carbamoyl, diethylcarbamoyl, phenylcarbamoyl), sulfonyl group (eg, methylsulfonyl, benzenesulfonyl), sulfinyl group (eg, methylsulfinyl, phenyl) Rufiniru), alkyloxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (e.g.,
Phenoxycarbonyl), an acyl group (for example, acetyl, benzoyl, formyl, pivaloyl), an acyloxy group (for example, acetoxy, benzoyloxy), a phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide), an alkylthio group (for example, , Methylthio, ethylthio), arylthio groups (for example, phenylthio groups), cyano groups, sulfo groups, carboxyl groups, hydroxy groups, phosphono groups, and nitro groups. The more preferable substituent of R is a halogen atom, an alkyl group, an aryl group, a 5- or 6-membered heterocyclic group containing at least one O, N or S,
An alkoxy group, an aryloxy group, an acylamino group, a sulfamoyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryloxycarbonyl group, an acyl group, a sulfo group, a carboxyl group, a hydroxy group and a nitro group. A particularly preferred substituent of R is a hydroxy group, a carbamoyl group, a lower alkylsulfonyl group or a sulfo group (including a salt thereof) when substituting an alkylene group, and a sulfo group (including a salt thereof) when substituting a phenylene group. Including).

The compound of formula (II) of the present invention is preferably a compound represented by formula (IV) or formula (V) shown below. The compound represented by formula (IV) represented by Chemical formula 11 of the present invention will be described.

[0044]

[Chemical 11] In the formula (IV), R21 represents an electron-withdrawing group, and R22 represents a hydrogen atom or a substitutable group. n2 represents an integer of 1 to 6, and n2 is preferably an integer of 1 to 3,
1 or 2 is particularly preferable. The electron withdrawing group represented by R21 is preferably Hammett's σ _p or σ _m or σ _I.
Is an organic group having a value of greater than 0. Hammett's σ _p value or σ _m value is “Structure-activity relationship of drugs” (published by Nankendo)
The page (1979) and the σ _I value are shown on page 105, and can be selected based on this table. R21 is preferably, for example, a halogen atom (eg, fluorine, chlorine, bromine, etc.), trichloromethyl group, cyano group, formyl group, carboxylic acid group, sulfonic acid group, carbamoyl group (eg, unsubstituted carbamoyl, diethylcarbamoyl). ), Acyl group (eg, acetyl group, benzoyl group), oxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group), sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.), sulfonyloxy group (eg, methane) Sulfonyl group), carbonyloxy group (for example, acetoxy group), sulfamoyl group (for example, unsubstituted sulfamoyl group, dimethylsulfamoyl group), heterocyclic group (for example, 2-thienyl group, 2-benzoxazolyl group, 2-
Benzothiazolyl group, 1-methyl-2-benzimidazolyl group, 1-tetrazolyl group, 2-quinolyl group). The carbon-containing group of R21 is preferably 1 to 20.
Including carbon. As the examples of the substitutable group represented by R22, those enumerated as the substituents of R are directly applicable. It is preferable that more than half of R22 contained in the compound of the formula (IV) are hydrogen atoms. Multiple R22s in the molecule
May be the same or different. R21 and R22 may be further substituted, and preferable substituents are R
Those enumerated as the substituents of. Also, R21
And R22, or two or more R22 are combined to form 3 to 6
A member ring may be formed. Next, the compound represented by the formula (V) represented by Chemical formula 12 of the present invention will be described.

[0045]

[Chemical 12] In the formula (V), R31 is R33 O-group, R33 S-group, (R33)
₂ N-group, (R33) ₂ P-group or phenyl,
R33 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 3 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, It represents a heterocyclic group having 4 to 30 carbon atoms. R31
Represents a (R33) ₂ N-group or a (R33) ₂ P-group,
The two R33 groups may be the same or different. R31 is preferably an R33 O- group. R32 and n3 have the same meaning as R22 in formula (IV), and a plurality of R32 may be the same or different. As the examples of the substitutable group represented by R 32, those enumerated as the substituents of R are directly applicable. R32 is preferably a hydrogen atom. n3 is preferably 1, 2, 4 or 5 and 2
Is particularly preferable. R31 and R32 may be further substituted, and preferable substituents include those enumerated as the substituents of R. In addition, R31 and R32, or two or more R32 may be bonded to form a ring.

Specific examples of the compounds represented by formula (II), formula (IV) and formula (V) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

[0053]

[Chemical 19] The iodide ion-releasing agent of the present invention can be synthesized according to the following synthetic method.

J. Am. Chem. Soc. , 76 , 3
227-8 (1954), J. Org. Chem. , 1
6 , 798 (1951), Chem. Ber. , 97 ,
390 (1964), Org. Synth. , V, 47
8 (1973), J. Am. Chem. Soc. , 1951 ,
1851, J.M. Org. Chem. , 19 , 1571
(1954), J. Chem. Soc. , 1952 , 1
42, J. Chem. Soc. , 1955 , 1383,
Angew, Chem. , Int. Ed. , 11 , 22
9 (1972), Chem. Commu. , 1971 ,
1112.

The iodide ion-releasing agent of the present invention releases iodide ions by reaction with an iodide ion-releasing regulator (base and / or nucleophile), and the nucleophile used at this time is preferably The following chemical species are listed. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, Examples thereof include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines and sulfides. In the present invention, the release rate and timing of iodide ions can be controlled by controlling the concentrations of bases and nucleophiles, the method of addition, and the temperature of the reaction solution. The base is preferably alkali hydroxide. The preferred concentration range of the iodide ion-releasing agent and the iodide ion-releasing agent used for rapidly generating iodide ions is 1 × 10 ^{−7 to} 20 M, more preferably 1 × 10 ^{−5 to} 10 M, and further Preferably 1 × 10 ^{−4 to} 5
M, particularly preferably 1 × 10 ^{−3 to} 2M. Concentration is 2
When it exceeds 0 M, the iodide ion-releasing agent having a large molecular weight and the added amount of the iodide ion-releasing agent become too large with respect to the capacity of the grain forming container, which is not preferable. Also, 1 × 1
When it is below 0 ^-7 , the reaction rate of iodide ion release becomes slow,
It is not preferable because it is difficult to rapidly generate the iodide ion-releasing agent.

The preferred temperature range is 30-80 ° C.
More preferably 35 to 75 ° C, particularly preferably 35 to 6
It is 0 ° C.

When the temperature is higher than 80 ° C., the reaction rate of iodide ion release generally becomes extremely high, and when the temperature is lower than 30 ° C., the reaction rate of iodide ion release generally becomes very slow. Absent.

In the present invention, when a base is used for releasing iodide ions, a change in liquid pH may be used. At this time, a preferable pH range for controlling the iodide ion release rate and timing is 2 to 12, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably the adjusted pH is 7. .5 to 10.0. p
Even under the neutral condition of H7, the hydroxide ion determined by the ionic product of water acts as a regulator.

Further, a nucleophile and a base may be used in combination,
At this time, the pH may be controlled within the above range to control the iodide ion release rate and timing.

The preferable range of the amount of iodide ions released from the iodide ion releasing agent is 0.1 to 20 mol% with respect to the total amount of silver halide, and more preferably 0.3 to.
15 mol%, particularly preferably 1 to 10 mol%,
You can choose according to your purpose. If it exceeds 20 mol%, the developing rate is generally delayed, which is not preferable. When the iodine atom is released from the iodide ion-releasing agent in the form of iodide ion,
All iodine atoms may be released, or some of them may remain without being decomposed. The iodide ion release rate from the iodide ion release agent will be specifically described with reference to examples.

In the present invention, for example, in the process of introducing a dislocation line into a tabular grain, it is necessary to form a silver halide phase containing silver iodide at the edge of the tabular grain while rapidly generating iodide ions. Is preferred for high density introduction. If the supply rate of iodide ions is too slow, that is, if the time for forming the silver halide phase containing silver iodide is too long, the silver halide phase containing silver iodide is redissolved during that time, and the dislocation line density is increased. Will decrease. On the other hand, it is preferable to slowly supply the iodide ion in order to form grains so that the dislocation dose distribution is not nonuniform among grains. Therefore, it is important to generate iodide ions rapidly without causing locality (non-uniform distribution). A region where iodide ion has a high locality is formed in the vicinity of this addition port when an iodide ion-releasing agent or an iodide ion-releasing regulator used together with it is added to the reaction solution in the grain forming container. This is because the iodide ion-releasing reaction is too fast with respect to the locality of the local concentration of the resulting additive. The time for the released iodide ions to deposit on the host grains is extremely fast, and grain growth occurs in the region near the addition port where iodide ion has a high locality, so that non-uniform grain growth occurs between grains. Therefore, it is necessary to select an iodide ion release rate that does not cause iodide ion locality. In the conventional method (for example, adding an aqueous solution of potassium iodide), the iodide ion is added in a free state even if the aqueous solution of potassium iodide is diluted and added. There is a limit even if we try to reduce it. That is, it has been difficult to form particles without unevenness between particles by the conventional method. However, the present invention capable of controlling the iodide ion release rate can reduce the locality of iodide ions as compared with the conventional method. In the above example, dislocation lines can be introduced between the grains more uniformly and at a higher density than in the conventional method by the present invention in which grains are formed while producing iodide ions rapidly and without causing locality. It became possible.

In the present invention, the iodide ion-releasing rate can be determined by controlling the temperature and the concentrations of the iodide ion-releasing agent and the iodide ion-releasing regulator as described above, and may be selected according to the purpose. In the present invention, the preferred iodide ion release rate is 100 to 50% of the total weight of the iodide ion-releasing agent present in the reaction solution in the grain forming vessel, and the iodide ion release rate is 180 seconds or less within 1 second or more. It is a rate of completion, more preferably a rate of completing release of iodide ions within 120 seconds, particularly preferably within 60 seconds. In the present invention, "within 180 consecutive seconds"
Is 180 during the continuous iodide ion release reaction.
It is within seconds, and the iodide ion release time may be measured by counting from any point during the continuous reaction.

When the iodide ion-releasing reaction period is divided into two or more times, it is calculated from any time point in the first iodide ion-releasing reaction period or any time point in the second or later iodide ion-releasing reaction period. Then, the iodide ion releasing rate from the iodide ion releasing agent present in the reaction solution at that time may be determined.

When the release rate of iodide ions exceeds 180 seconds, the release rate is generally slow, and when the release rate is less than 1 second, the release rate is too fast, so that the use conditions are limited. The amount of iodide ion released is 5
The same is true even if it is less than 0%. Further, the rate at which 100 to 70% of the iodide ion-releasing agent present in the reaction solution in the grain forming container completes the release of iodide ion within 180 consecutive seconds is more preferable, and further preferably 100
-80%, particularly preferably 100-90%, is the rate at which iodide ion release is completed within 180 consecutive seconds. Preferred in the present invention when the reaction for rapidly forming iodide ions is represented by a secondary reaction that is substantially proportional to the iodide ion-releasing agent concentration and the iodide ion-releasing regulator concentration (in water, 40 ° C.). Has a second-order reaction rate constant of 1000 to 5 × 10 ^-3 (M ^-1 · sec ^-1 ).
And more preferably 100 to 5 × 10 ^-2 (M ^-1
* Sec ^-1 ), particularly preferably 10 to 0.1
(M ^-1 · sec ^-1 ). The term "substantially second-order reaction" means that the correlation coefficient is 1.0 to 0.8.
Pseudo-first-order reaction in water at 40 ° C. with an iodide ion-releasing agent concentration of 10 ⁻⁴ to 10 ⁻⁵ M and an iodide ion-releasing regulator concentration of 10 ⁻¹ to 10 ⁻⁴ M. Typical second-order reaction rate constant k measured under conditions that can be regarded as
(M ⁻¹ · sec ⁻¹ ) is as follows. Compound number Iodide ion release regulator k 11 Hydroxide ion 1.3 1 Sulfite ion 1 × 10 ⁻³ or less 2 Ibid 0.29 58 Ibid 0.49 63 Ibid 1.5 22 Hydroxide ion 720 k is 1000 If it exceeds 5, the release will be too fast to control, and if it is 5 × 10 ⁻³ or less, it will be too slow to obtain the effect of the present invention.

In the present invention, the following method is preferable for controlling the release of iodide ions. That is, by changing the pH, the concentration of the nucleophilic substance, the temperature, etc., from the already uniformly distributed iodide ion-releasing agent added to the reaction solution in the grain forming container, it is usually possible to change the pH from low to high. It is a method of releasing the iodide ion while controlling it uniformly throughout the reaction solution. It is preferable to add an alkali for increasing the pH at the time of releasing iodide ions and a nucleophilic substance used in combination in a state where the iodide ion-releasing agent is evenly distributed throughout.

The emulsion grains of the present invention will be described below. The emulsion grains of the present invention are silver halide containing silver iodide. The emulsion grains of the present invention contain at least one of a silver iodide phase, a silver iodobromide phase, a silver chloroiodobromide phase and a silver chloroiodide phase.
Other silver salts such as silver rhodanide, 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 range of silver iodide content of the emulsion grains of the present invention is preferably 0.1 to 20 mol%, and more preferably 0.3 to 1.
It is 5 mol%, particularly preferably 1 to 10 mol%, but it may be selected according to the purpose. If it exceeds 20 mol%, the developing rate is generally delayed, which is not preferable.

The emulsion grains of the present invention preferably have the following structure based on the halogen composition. (1) In the case of a particle having one or more coating shells for a base particle, a double structure, a triple structure, a quadruple structure, a quintuple structure, ... It is preferably formed by using an iodide ion releasing method.

(2) In the case of particles in which one or more layers that are not completely covered by the base particles are deposited: two-layer structure, three-layer structure, four-layer structure, five-layer structure, ... The outermost layer is preferably formed by using the iodide ion releasing method of the present invention.

(3) In the case of grains epitaxially grown at selective sites of the base grain: The apex of the grain, the peripheral portion of the grain, and the epitaxial portion of the main plane portion of the grain are formed using the iodide ion releasing method of the present invention. It is preferable.

It is preferable that the composition of the coating shell of silver halide containing silver iodide formed by the method of releasing iodide ions of the present invention, the deposition layer and the epitaxial portion has a high silver iodide content. These silver halide phases may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but are preferably silver iodide or silver iodobromide, and are preferably silver iodide. It is more preferable that there is. In the case of silver iodobromide, the preferable silver iodide (iodide ion) content is 1 to 45 mol%,
More preferably 5 to 45 mol%, particularly preferably 10 to
It is 45 mol%. When the amount is less than 1 mol%, it is not preferable because it is difficult to obtain effects such as enhancement of dye adsorption, increase in intrinsic sensitivity, and formation of misfit required for introducing dislocation lines. 45 mol% is the solid solution limit of silver iodobromide.

It is preferred to prepare silver halide grains containing dislocation lines using the iodide ion releasing method of the present invention. A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between a region that has already slipped and a region that has not slipped yet. Regarding the dislocation lines of silver halide crystals,
1) C.I. R. Berry, J .; Appl. Phys. ，
27,636 (1956), 2) C.I. R. Berry,
D. C. Skillman, J .; Appl. Phys. ，
35, 2165 (1964), 3) J. F. Hamil
ton, Photo. Sci. Eng. , 11, 57 (1
967), 4) T.I. Shiozawa, J .; Soc. P
hot. Sci. Jap. , 34, 16 (1971),
5) T. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 35, 213 (1972) and the like, which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When directly observing dislocation lines using a transmission electron microscope, be careful not to apply pressure enough to generate dislocation lines on the grains, place the silver halide grains taken out from the emulsion on a mesh for electron microscope observation, The sample is observed by a transmission method in a cooled state so as to prevent damage (for example, printout) due to an electron beam. In this case, the thicker the particles, the more difficult it is for the electron beam to pass through. Therefore, the voltage type (for a thickness of 0.25 μm,
It can be observed more clearly by using an electron microscope of 200 kV or more). On the other hand, as the effect of dislocation lines on the photographic performance, G. C. Farnell, R.M. B.
Flint, J. B. Chapter, J. Photo.
Sci. , 13, 25 (1965), it is shown that in a large size high aspect ratio tabular silver halide grain, the place where the latent image nucleus is formed and the defect in the grain have a close relation. ing. JP-A-63-220
No. 238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocation lines are intentionally introduced. In these patent applications, it is shown that tabular grains having dislocation lines introduced therein are superior in photographic characteristics such as sensitivity and reciprocity law to tabular grains having no dislocation lines.

Here, a method for introducing dislocation lines into silver halide grains will be described. In the present invention, it is preferable to introduce dislocation lines into the silver halide grains as follows. That is, a base silver halide grain is prepared, and a silver halide phase containing silver iodide (the above-described silver halide coating shell, a deposition layer, and an epitaxial growth) is formed on the base grain. As described above, the higher the silver iodide content of these silver halide phases, the more preferable. Base grain has a silver iodide content of 0
It is preferably ˜15 mol%, more preferably 0
The amount is ˜12 mol%, particularly preferably 0 to 10 mol%, but it may be selected according to the purpose. If it exceeds 15 mol%, the developing rate is generally delayed, which is not preferable.

The amount of halogen added to form this high silver iodide content phase on the base grain is 2 times the silver amount of the base grain.
-15 mol% is preferable, 2-10 mol% is more preferable, and 2-5 mol% is particularly preferable, but it may be selected according to the purpose. If it is less than 2 mol%, dislocation lines are less likely to be introduced, which is not preferable. When it exceeds 15 mol%, the developing rate is delayed, which is not preferable. At this time, the high silver iodide content phase is preferably present in the range of 5 to 80 mol%, more preferably 10 to 70 mol%, and particularly preferably 20 to 60 mol% based on the total amount of silver. Is to exist within the range of. If it is less than 5 mol% or more than 80 mol%, it is difficult to obtain high sensitivity by introducing dislocation lines, which is not preferable.
The high silver iodide content phase may be formed on the base grain at any place, and it may be formed on the base grain or only on a specific site. It is preferable to control the position of the dislocation lines within. At that time, the composition of the halogen to be added, the addition method, the temperature of the reaction solution, pAg, the solvent concentration, the gelatin concentration, the ionic strength, etc. may be freely selected and used. The dislocation lines can then be introduced by forming a silver halide shell outside these phases. The composition of the silver halide shell may be any of silver bromide, silver iodobromide and silver chloroiodobromide, but silver bromide or silver iodobromide is preferred. In the case of silver iodobromide, the silver iodide content is preferably 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, most preferably 0.1 to 10 mol%.
It is 3 mol%. If it is less than 0.1 mol%, it is difficult to obtain effects such as enhancement of dye adsorption and development acceleration, which is not preferable.
When it exceeds 12 mol%, the developing rate is delayed, which is not preferable.

The preferred temperature in the process of introducing the dislocation lines is 30 to 80 ° C., more preferably 35 to 75.
C., particularly preferably 35 to 60.degree. In order to control the temperature at a low temperature of less than 30 ° C. or a high temperature of more than 80 ° C., a high-capacity manufacturing apparatus is required, which is not preferable in manufacturing. Moreover, preferable pAg is 6.4 to 10.5.
In the case of tabular grains, the position and the number of dislocation lines for each grain when viewed from the direction perpendicular to the principal plane can be determined from the photograph of the grain photographed with an electron microscope as described above. Since dislocation lines may or may not be seen depending on the tilt angle of the sample with respect to the electron beam, in order to observe the dislocation lines without omission, the particle images of the same grain at as many sample tilt angles as possible should be observed. It is necessary to find the location.

In the present invention, it is preferable to determine the existence position and the number of dislocation lines by changing the tilt angle for the same grain in 5 ° steps using five types of grain photographs using a high-voltage electron microscope.

When dislocation lines are introduced into the tabular grains in the present invention, the positions thereof can be selected from, for example, limiting to the apex portion and the fringe portion of the grain, or introducing into the entire main plane portion. However, it is particularly preferable to limit to the fringe portion. The fringe portion as referred to in the present invention refers to the outer periphery of the tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a point which is first seen from the side is the grain. The point outside the point where the average silver iodide content of the whole is exceeded or below. In the present invention, it is preferable to introduce dislocation lines into the silver halide grains with high density. When introducing dislocation lines in tabular grains,
When the number of dislocation lines is counted by the above-mentioned method using an electron microscope, tabular grains having 10 or more dislocation lines per grain in the grain fringe portion are preferable, more preferably 30 or more, and particularly preferably 50 or more. Is. When the dislocation lines are densely present or when the dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However,
Even in these cases, about 10, 20, 30
It can be counted as a book. It is desirable that the dislocation dose distribution among silver halide grains is uniform. In the present invention, when dislocation lines are introduced into tabular grains, tabular grains having 10 or more dislocation lines in each grain fringe portion account for 100 to 50% (number) of all grains.
It is preferable to occupy 100% to 70%, more preferably 100 to 70%, and particularly preferably 100 to 90%. When it is less than 50%, it is not preferable in terms of homogeneity between particles. In the present invention, when determining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains, more preferably 200 grains or more, and particularly preferably 300 grains or more. Observe and ask.

The tabular grain of the present invention is a silver halide grain having two parallel main planes facing each other. The tabular grains of the present invention have one twin plane or two or more parallel twin planes.

The twin plane is the (111) plane on both sides of which ions at all lattice points have a mirror image relationship.
It refers to a surface. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape, and have outer surfaces parallel to each other.

The equivalent circle diameter of the tabular grains of the present invention is preferably 0.3 to 10 μm, more preferably 0.4 to 5 μm, and particularly preferably 0.5 to 4 μm.

If it is less than 0.3 μm, the merit of tabular grains cannot be fully utilized, which is not preferable. When it exceeds 10 μm, the pressure property is deteriorated, which is not preferable.

The grain thickness of the tabular grain of the present invention is 0.
The thickness is preferably 05 to 1.0 μm, more preferably 0.08 to 0.5 μm, and particularly preferably 0.08 to
It is 0.3 μm. When it is less than 0.05 μm, the pressure property is deteriorated, which is not preferable. When it exceeds 10 μm, the merit of tabular grains cannot be fully utilized, which is not preferable.

The aspect ratio of the tabular grains of the present invention is preferably 2 to 30, more preferably 3 to 2.
5, most preferably 5 to 20. When it is less than 2, the merit of tabular grains cannot be fully utilized, which is not preferable. When it exceeds 30, the pressure property is deteriorated, which is not preferable.

The aspect ratio is a value obtained by dividing the circle equivalent diameter of the projected area of a silver halide grain by the grain thickness. As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by the replica method and determining the equivalent circle diameter and thickness of the projected area of each particle. In this case, the thickness is calculated from the length of the shadow of the replica. In the present invention, hexagonal tabular grains 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 to 1 are used in the emulsion. 100 to 5
It is preferably 0%, more preferably 100 to 70%, particularly preferably 100 to 90%.

The emulsion of the present invention is preferably monodisperse.

The variation coefficient of the grain size distribution of all silver halide grains of the present invention is preferably 20% to 3%, more preferably 15% to 3%, particularly preferably 10%.
To 3%. If it exceeds 20%, it is not preferable in terms of homogeneity between particles.

The coefficient of variation of the particle size distribution is a value obtained by dividing the standard deviation of the particle size distribution of the particles by the average particle size.

Further, it is preferable to prepare the outermost shell near the surface of the silver halide grain by using the iodide ion releasing method of the present invention. Forming a silver halide phase containing silver iodide near the grain surface is important from the viewpoint of enhancing the dye adsorbing power and controlling the developing rate. In the present invention, these can be controlled by selecting the silver iodide content of the silver halide phase of the outermost shell near the grain surface according to the purpose.

It is desirable that the halogen composition on the surface of the grains be uniform among grains, and the present invention achieves the uniformity between grains that cannot be reached by the conventional techniques. In the present invention, the particle surface means a region from the surface to a depth of about 50 Å. The halogen composition in such a region can be measured by a surface analysis method such as XPS (X-ray photoelectron spectroscopy) method or ISS (ion scattering spectroscopy) method. In the present invention, the silver iodide content of the silver halide phase on the grain surface of the emulsion grains measured by these surface analysis methods is 0.
1 to 15 mol% of silver halide grains is preferable, more preferably 0.3 to 12 mol%, and particularly preferably 1 to 10 mol%.
Mol%, most preferably 3 to 8 mol%. Further, it is desirable that the halogen composition of the entire grains be uniform among the grains.

In the present invention, the variation coefficient of the silver iodide content distribution among individual emulsion grains is preferably 20% to 3%, more preferably 15% to 3%, and particularly preferably 10% to 10%. 3%. The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The variation coefficient of the silver iodide content distribution is a value obtained by dividing the variation (standard deviation) of the silver iodide content of each grain by the average silver iodide content.

The following is a description of the emulsion of the present invention and the 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 iodobromide and silver chloroiodobromide. Other silver salts such as silver rhodanide, 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 structure in terms of halogen composition in its grains. Typical examples thereof are JP-B-43-13162 and JP-A-6-6.
No. 1-215540, JP-A-60-222845, JP-A-60-143331, JP-A-61-75337, etc. The core-shell having a halogen composition in which the inside and the surface of the grain are different from each other. Type or double structure type particles. Also, it is not a simple double structure,
A triple structure as disclosed in 0-222844,
Alternatively, it is possible to form a multilayer structure of more than that, or to thin the silver halide having a different composition on the surface of the core-shell double structure grain. In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are JP-A-59-133540, JP-A-58-108526, and European Patent 199,290A2.
Japanese Patent Publication No. 58-24772, Japanese Patent Laid-Open No. 59-1625.
No. 4 and the like. The crystal to be bonded can be generated by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure. In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan and silver carbonate may be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as lead oxide may be used as long as a joint structure is possible. In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core portion and a high shell portion are preferable. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of the particles having these structures may be a clear boundary or an unclear boundary. In addition, a positive aspect in which the composition is positively and continuously changed is also a preferred embodiment. In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable. Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. 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 content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, (100) plane and (1
This is the case where the halogen composition is changed only on one surface of the tetrahedral grain 11), or on one of the main plane and the side surface of the tabular grain.

The silver halide grains used in the emulsion of the present invention and the emulsions other than the present invention which are used in combination therewith, even if they are normal crystals not containing twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photograph ( Corona), P. 163, eg, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, JP-B-55-42737, and JP-A-60-
The dodecahedron grains having the (110) plane disclosed in No. 222842 can be used. Furthermore, Jou
rnal of ImagingScience 30
Volume 247 pages (h11) plane particles typified by (211) as reported in 1986, (331)
Is a typical (hh1) plane particle, the (210) plane is a typical (hk0) plane particle and the (321) plane is a typical (hk) plane particle.
1) The surface particles also require a devised preparation method, but can be selected and used according to the purpose. A tetrahedral particle in which the (100) plane and the (111) plane coexist in one particle, a particle in which the (100) plane and the (110) plane coexist, or a particle in which the (111) plane and the (110) plane coexist. Particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of more than 1 can be used in the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleeve (Cleve, Photography Theo).
ry and Practice (1930)), 13
Page 1: Gatov, Photographic Science and Engineering (Gutoff, Photogr
apic 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 tabular grains can be selected from triangles, hexagons, circles, and the like. 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.

As the grain size of tabular grains, a circle-equivalent diameter of the projected area is often used.
The average diameter as described in No. 8,106 is 0.6
Particles of μm or less are preferable for high image quality. An emulsion having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617 is also preferable. It is preferable to increase the sharpness by limiting the grain thickness of the tabular grains to 0.5 μm to 0.05 μm, and more preferably 0.3 μm to 0.05 μm. Furthermore, an emulsion having a high uniformity of thickness with a variation coefficient of grain thickness of 30% to 3% is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select a dislocation or a curved dislocation introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only in a specific part of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges. The silver halide emulsion used in the present invention is described in European Patent Nos. 96,727B1 and 64,4.
12B1 and other treatments for rounding particles, or West German Patent No. 2,306,447C
No. 2, JP-A-60-221320, the surface may be modified. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. A part of the crystal described in JP-A-58-106532 and JP-A-60-221320, for example, a method of forming a hole at the apex or the center of the surface, or 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 measured by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less, and coarse particles having a diameter of more than 10 μm. It is preferable to use grains of 0.1 μm or more and 3 μm or less 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, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% to 3%, more preferably 20% to 3%, still more preferably 15% to 3%. In some cases, the monodisperse emulsion is defined as a grain size distribution such that 80% to 100% of all grains fall within ± 30% of the average grain size in terms of number of grains or weight. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used. The emulsion of the present invention and photographic emulsions other than the present invention which are used in combination therewith are described in "Physics and Chemistry of Photography" by Graphide, published by P. Monteflac (P. Glafkides,
Chemie et Phisique Photog
Raphique, Paul Montel, 196
7), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographi.
c Emulsion Chemistry (Foca
L Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press, Inc. (V.L.
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 halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the double jet method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

A method of adding silver halide grains which have been previously 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 may be selected from total addition at once, addition in plural times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface. A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,1.
42,900, European Patents 273,429 and 27
No. 3,430, West German Laid-Open Patent No. 3,819,241 and the like are effective particle forming methods. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion. 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
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 supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is. A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is disclosed in US Pat.
6,287, 3,342,605, 3,4
No. 15,650, No. 3,785,777, West German Laid-Open Patent Nos. 2,556,885, and No. 2,555,364 can be selected and used. Silver halide solvents are useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. The total amount of these ripening agents can be compounded in the dispersion medium in the reactor before adding the silver and halide salts, and the halide salt, silver salt or peptizer can be added in the reactor as well. Can also be introduced. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages. As the ripening agent, for example, ammonia, thiocyanate (eg, rhodan potassium, rhodan ammonium), organic thioether compound (eg, US Pat. Nos. 3,574,628 and 3,021,215)
No. 3,057,724, No. 3,038,80
No. 5, No. 4,276, 374, No. 4, 297, 4
No. 39, No. 3,704, 130, No. 4,782
013, compounds described in JP-A-57-104926. ), A thione compound (for example, JP-A-53-8240).
No. 8, 55-77737, U.S. Pat. No. 4,221,
No. 863, the tetra-substituted thiourea, the compounds described in JP-A No. 53-144319), and the silver halide grains described in JP-A No. 57-202531, which can promote the growth of the silver halide grains. Examples thereof include mercapto compounds and amine compounds (for example, JP-A-54-100717). Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal,
A variety of synthetic hydrophilic polymeric substances such as single or copolymers such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo
o. Japan. No. 16. An enzyme-treated gelatin as described in P30 (1966) may be used, and
A hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for washing can be selected according to the purpose, but it is preferably selected in the range of 5 ° C to 50 ° C. Although the pH during washing can be selected according to the purpose, 2
It is preferable to select between 10 and 10. More preferably 3
The range is from -8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. 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, hydrates, 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, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

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 (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, K)
It is also possible to add it to Br, KI) and continuously add it during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present. The silver halide grains of the present invention are subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization at any step of the silver halide emulsion production process. be able to. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. A type in which chemically sensitized nuclei are embedded inside the grain, a type in which it is embedded at a shallow position from the grain surface,
Alternatively, there is a type that makes a chemically sensitized nucleus on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface. One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination.
es), The Photographic Process, 4th
Edition, published by Macmillan, 1977, (TH Jame
s, The Theory of the Photo
graphic Process, 4th ed, Ma
cmillan, 1977) 67-76, and using active gelatin, and Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, 3;
Volume 4, June 1975, 13452, U.S. Pat. No. 2,6.
42,361, 3,297,446, 3,
No. 772, 031, No. 3,857,711, No. 3,
901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
No. 5,755, pAg 5-10, pH 5-
8 and a temperature of 30-80 ° C. can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are R ₂ PdX ₆ or R ₂ PdX ₄
It is represented by. Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
The sulfur-containing compounds described in Nos. 57,711, 4,266,018 and 4,054,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,75
7, JP-A-58-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. The emulsion of the present invention is preferably combined with gold sensitization.
The preferred amount of gold sensitizer is 1 per mol of silver halide.
The amount is from × 10 ^-4 to 1 × 10 ^-7 mol, and more preferably from 1 × 10 ^{-5 to} 5 × 10 ^-7 mol. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 . The amount of the sulfur sensitizer used for the silver halide grains of the present invention is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ⁻⁵ to 1 mol per mol of the silver halide. It is 5 × 10 ⁻⁷ mol. Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones , Selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere of pAg 1 to 7 called silver ripening, a pH of 8 to 8 called high pH ripening. Any of the methods of growing or aging in 11 high pH atmosphere can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. Known examples of reduction sensitizers include 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, or two or more kinds of compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferable 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 it at an appropriate time during grain growth is preferred. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions 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. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, 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 ), peroxy complex compound (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 highly valent metals (eg potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-.
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. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Chitraazaindenes), known as antifoggants or stabilizers such as pentaazaindenes,
Many compounds can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,947,
Those described in Japanese Examined Patent Publication No. 52-28660 can be used. One of the preferable compounds is JP-A-63-21.
There are compounds described in 2932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is represented by the chemical formula 1 above.
In order to exert the effect of the present invention, it is preferable to use in combination with the spectral sensitizing dye represented by the formula (I) to be spectrally sensitized with methine dyes and the like. The dyes used include
Cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a dye belonging to a merocyanine dye and a composite merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole A nucleus, a benzimidazole nucleus, and a quinoline nucleus can be applied. 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. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617, 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, British 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 emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
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 of the sensitizing dye can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, but the more preferable silver halide grain size is 0.2 to
In the case of 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective.

The above-mentioned various additives are used in the light-sensitive material of the present invention, but in addition to them, various additives can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (1978).
December 18), Item 18716 (1 January 1979)
January) and Item 308119 (December 1989), and the relevant parts 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 24 648 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 Page left column UV absorber 7 Stain inhibitor 25 page right column 650 Left to right column 1002 right 8 Dye image stabilizer page 25 1002 right 9 Hardener 26 page 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 Surfactant 13 static page 27 same as above 1006 right to 1007 left antistatic agent 14 matting agent 1008 left to 1009 left Photosensitive material produced using the silver halide emulsion obtained in the present invention Need only be at least one of a silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer provided on a support, and a silver halide emulsion layer and a non-photosensitive layer are provided. The number of layers and the order of layers are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Are sequentially arranged from the support side in the order of a red color-sensitive layer, a green color-sensitive layer and a blue color-sensitive layer. 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 in the same color-sensitive layer.

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. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

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

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in the specification No. 6, it is also possible to provide the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest 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 configurations and arrangements can be selected according to the purpose of each light-sensitive material.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the related portions are shown below.

Additive type RD17643 RD18716 RD307105 (1978.12) (1979.11) (1989.11) 1 Chemical sensitizer page 23 648 page right column 866 page 2 sensitivity enhancer page 648 right column 3 spectral sensitizer, page 23-24 648 Page right column ~ 866 ~ 868 Supersensitizer 649 page Right column 4 Whitening agent Page 24 647 Page right column 868 Page 5 Antifoggant, page 24 ~ 25 649 Page right column 868 ~ 870 and stabilizer 6 Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7 stain inhibitor page 25, right column, page 650, left column to page 872, right column 8 dye image stabilizer page 25, 650 Page left column 872 Page 9 Hardener 26 page 651 Page left column 874 to 875 page 10 Binder page 26 651 Page left column 873 to 874 page 11 Plasticizer and lubricant page 27 650 page right column 876 page 12 Coating aid, Page 26 to 27 Page 650 Right column 875 to 876 Surfactant 13 Static Page 27 650 Page right column 876 to 877 Anti-stop agent 14 Matting agent 878 to 879 Page In order to prevent deterioration of true performance, a compound capable of immobilizing by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 may be added to a light-sensitive material. preferable. The light-sensitive material of the present invention can be incorporated into US Pat.
40,454, 4,788,132, JP-A-6
It is preferable to contain the mercapto compound described in No. 2-18539.

The light-sensitive material of the present invention can be prepared by the method described in JP-A-1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO088.
Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to include the dyes described in No.

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-C to G.

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

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, 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, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue 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,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

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 (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 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.
DIR couplers that release development inhibitors are described in RD1 above.
7643, section VII-F and ibid. 307105, VII-
Patents described in section F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154,234, 60-184,248, 63-37,346, 63-37,350, and U.S. Pat.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,093
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
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. , RD. No. 1
1449, 24241, and bleaching accelerator releasing couplers described in JP-A No. 61-201247, U.S. Pat.
55,477, etc., a coupler releasing a leuco dye described in JP-A-63-75747, and a coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described, for example, in 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); hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) can be exemplified. The auxiliary solvent has, for example, a boiling point of about 30 ° C or higher, preferably 50 ° C.
An organic solvent having a temperature of not less than about 160 ° C. and not more than about 160 ° C. can be used, and typical examples thereof include 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.
No. 9,363, West German Patent Application (OLS) No. 2,541,
No. 274 and No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-125747.
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. Representative examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention can be particularly preferably used for a film for color duplication.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 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 is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness here means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, for example, A. Green et al., Photography Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129. In addition, T _1/2 is a color developing solution of 30
The maximum swollen film thickness reached when treated at 3 ° C for 15 minutes
0% is defined as the saturated film thickness, which is defined as the time required to reach 1/2 of the saturated film thickness.

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

The 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 preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. .. The swelling ratio of this back layer is preferably 150 to 500%.

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

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, 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 their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in 2
It is also possible to use together more than one species.

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, 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 processing is carried out, black and white development is usually carried out before color development. This black-and-white developer contains, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-, for example.
Known black-and-white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. P of these color developers and black and white developers
H is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the 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 represented 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, the movable lid described in JP-A-1-82033 is used. And the slit development processing method described in JP-A-63-216050. Reducing the aperture ratio is preferably applied not only in both the color development and black and white development steps but also in the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilizing. 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. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, the bleaching treatment after the bleach-fixing treatment can be arbitrarily carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids (in particular, sodium persulfate is suitable for color negative films for motion pictures), quinones, and nitro compounds are used. As a typical bleaching agent, an organic complex salt 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 ether diaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Complex salts of can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A No. 51-140129, a thiazolidine derivative described in JP-A No. 51-140129;
832, 53-32735, and U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561, West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40943, JP-A-49-59644,
53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95630 are preferred. Further, the compounds described in US 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 a color light-sensitive material 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. A particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specific examples thereof 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, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Also, with thiosulfate, for example, thiocyanate,
A combined use of a thioether compound and thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 2
The sulfinic acid compounds described in No. 94,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

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, 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 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, or a stirring means using a rotating means in JP-A-62-183461 is used. There are ways to increase the effect. Furthermore, a method of further improving the stirring effect by moving the photosensitive material while making the emulsion surface contact with the wiper blade provided in the solution and making the emulsion surface turbulent, and increasing the circulation flow rate of the entire processing solution There is a method of making it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the agitation improving means is more effective when a bleaching accelerator is used, and the accelerating effect can be remarkably increased, and the fixing inhibiting effect can be eliminated by the bleaching accelerator.

Automatic developing machines used for developing the light-sensitive material of the present invention are disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), application,
Furthermore, 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 various conditions such as a replenishment method such as counterflow and forward flow. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
the Society of Motion Pi
movie and Television Engi
neers Vol. 64, p. 248-253 (1955
May issue).

According to the multi-stage countercurrent method described in the above document,
Although the amount of washing water can be greatly reduced, bacteria are propagated due to an increase in the residence time of water in the tank, and the resulting 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. Further, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorine-based germicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Sanitary Technology "Sterilization, sterilization and antifungal technology of microorganisms" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal It is also possible to use the fungicide described in "Molding Encyclopedia" (1986).

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 set variously depending on, for example, the characteristics of the light-sensitive material and the use, but generally 15 to 45 ° C. and 20 seconds to 1
A range of 0 minutes, preferably 25 to 40 ° C. and 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can 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 stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

For example, in processing using an automatic processor,
When each of the above 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. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, such as Research Disclosure No. 3,342,599. 14, 850 and the same No.
Schiff base type compounds described in Nos. 15 and 159, No. 1
Aldol compounds described in US Pat.
Metal salt complexes described in JP 719,492, JP-A-53-1.
The urethane compound described in No. 35628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, 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 is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

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, European Patent No. 210,660A2 and the like can be applied to the photothermographic material.

The silver halide color photographic light-sensitive material of the present invention is described in JP-B-2-32615 and JP-B-3-397.
When applied to the lens-equipped film unit described in No. 84 etc., it is more effective and more effective.

[0171]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 Tabular silver iodobromide emulsion (1) Preparation of emulsion Tabular silver iodobromide core emulsion 1-A An aqueous solution containing 6.2 g of gelatin and 6.4 g of KBr 12
Stirring while keeping 00cc at 60 ° C., 1.9M Ag
8 cc of NO ₃ aqueous solution and 9.6 c of 1.7 M KBr aqueous solution
c was added with a double jet for 45 seconds. Gelatin 38
After adding g, the temperature was raised to 75 ° C. and the temperature was adjusted to 20 in the presence of NH _3.
Aged for minutes. After neutralization with HNO ₃ , 1.9M AgNO
₃ aqueous solution 405 cc and KBr aqueous solution containing 5 mol% of KI were added for 87 minutes while accelerating the flow rate while keeping the pAg at 8.44 (the flow rate at the end is 10 times that at the start). Thereafter, this emulsion was cooled to 35 ° C. and desalted by a conventional flocculation method. The obtained silver iodobromide emulsion was a tabular grain having an average equivalent circle diameter of 1.8 μm, an average thickness of 0.26 μm and an average aspect ratio of 7.

Tabular Silver Iodobromide Emulsion 1-B Emulsion 1 containing 164 g of AgNO ₃ equivalent to silver iodobromide
-A was added to 1950 cc of water, temperature was 55 ° C, pAg
Was maintained at 8.9 and the pH was maintained at 5.0. Then 0.32M
KI aqueous solution was added quantitatively for 1 minute, and then 1.9M
206 cc of AgNO ₃ solution and 2.0 M of KBr aqueous solution were added over 36 minutes so as to keep the pAg at 8.9. After this, desalting was carried out by a conventional flocculation method. The obtained silver iodobromide emulsion was a tabular grain having an average equivalent circle diameter of 2.1 μm, an average thickness of 0.34 μm and an average aspect ratio of 6,
The same applies to the following emulsions 1-C to 1-H.

Tabular silver iodobromide emulsion 1-C was prepared in the same manner as emulsion 1-B except for the following.

Instead of adding the KI aqueous solution, a silver iodide fine grain emulsion having an average grain size of 0.02 μm corresponding to AgNO ₃ (6.8 g) prepared separately was added and dissolved.

Tabular silver iodobromide emulsion 1-D was prepared in the same manner as emulsion 1-B except for the following.

Instead of adding an aqueous KI solution, 2-iodoethanol (3.1 cc) was added, and then an aqueous NaOH solution was added to raise the pH to 9.5 and kept for 10 minutes to rapidly generate iodide ions. After soaking, it was returned to 5.0.

Tabular silver iodobromide emulsion 1-E was prepared in the same manner as emulsion 1-D except for the following.

After adding 2-iodoethanol (3.1 cc), an aqueous NaOH solution was added to raise the pH to 10.5 and kept for 4 minutes to rapidly generate iodide ions, and then to 5.0. I brought it back.

Tabular silver iodobromide emulsion 1-F was prepared in the same manner as emulsion 1-B except for the following.

Instead of keeping the temperature at 55 ° C, it was kept at 40 ° C.

Instead of adding an aqueous KI solution, sodium p-iodoacetamidobenzenesulfonate (15.
3 g) After adding an aqueous solution, a 0.80 M sodium sulfite aqueous solution (75 cc) was added, and a NaOH aqueous solution was added to raise the pH to 9.0 and hold for 10 minutes to rapidly generate iodide ions. , Back to 5.0.

Tabular silver iodobromide emulsion 1-G was prepared in the same manner as emulsion 1-B except for the following.

Instead of adding an aqueous KI solution, sodium p-iodoacetamidobenzenesulfonate (15.
3 g) aqueous solution was added, and then 0.80 M sodium sulfite aqueous solution (60 cc) was added to raise the pH to 9.0 and hold for 8 minutes, and then returned to 5.0.

Tabular silver iodobromide emulsion 1-H was prepared in the same manner as emulsion 1-F except for the following.

Instead of keeping the temperature at 40 ° C, it was kept at 55 ° C.

Tabular Silver Iodobromide Emulsion 1-I (Comparative Emulsion) It was prepared in the same manner as Emulsion 1-B except for the following.

Instead of adding the KI aqueous solution, an iodoacetic acid (7.5 g) aqueous solution was added, and then a NaOH aqueous solution was added to raise the pH to 10.5 and held for 15 minutes to gradually release the iodide ion. After that, it was returned to 5.0. (2) Chemical Sensitization Emulsions 1-B to 1-H were subjected to gold and sulfur sensitization so that the sensitivity became highest when exposed to 1/100 ″.

Then, as shown in Table 1, a sensitizing dye (4.0
× 10 ⁻⁴ mol / mol Ag) was added. (3) Preparation of coated sample and its evaluation On the cellulose triacetate film support provided with an undercoat layer, the emulsion and the protective layer were coated in the coating amounts as shown below to obtain coated samples S-1 to S-10. Created. 1. Emulsion coating conditions <Emulsion layer> -Emulsion ... Various emulsions (silver 3.6 x 10 ^-2 mol / m ² ) -Coupler (1.5 x 10 ^-3 mol / m ² ).

[0189]

[Chemical 20] - tricresyl phosphate (1.10g / m ²⁾ · Gelatin (2.30g / m ²⁾ <Protective Layer> 2,4-dichloro-6-hydroxy -s- triazine sodium salt (0.08 g / m ² ) ・ Gelatine (1.80 g / m ² ) These samples were placed under the conditions of 40 ° C. and 70% relative humidity for 14 days.
After standing for a period of time, the film was exposed through a continuous wedge for 1/100 second, and the following color development was performed. 2. Exposure / processing conditions The density of the processed sample was measured with a green filter.

Step Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C. Bleach fixing 3 minutes 00 seconds 40 ° C. Water washing (1) 20 seconds 35 ° C. Water washing (2) 20 seconds 35 ° C. stability 20 seconds 35 ° C. Drying 50 seconds 65 ° C. Next, the composition of the treatment liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethyl 4.5 amino) -2-methylaniline sulfate Water was added to 1.0 L pH 10.05 (bleach-fixing solution) ( Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleach acceleration Agent 0.01 mol

[0191]

[Chemical 21] 1.0 L pH 6.0 (aqueous solution) by adding water to H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And OH type anion exchange resin (the same Amberlite IR-
400) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and then 20 mg of sodium isocyanurate dichloride.
/ L and 1.5 g / L sodium sulfate were added.

The pH of this liquid is in the range of 6.5-7.5. (Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl 0.3 ether (average degree of polymerization: 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added 1. 0L pH 5.8-8.0 Sensitivity was expressed as the relative value of the logarithm of the reciprocal of the exposure amount expressed in lux · sec which gives a density of 0.2 on fog.

Regarding the pressure characteristics, the pressure characteristics were tested by the following test method A. Then, exposure for sensitometry was given and the above-mentioned color development was performed. Test method A After placing in an atmosphere with a relative humidity of 55% for 3 hours or more, a load of 4 g was applied with a needle having a thickness of 0.1 mmφ in the same atmosphere,
Test method for scratching the emulsion surface at a speed of 1 cm / sec. The developed sample was measured with a measurement slit of 5 μm × 10 mm to measure the densities of the pressed portion and the unpressed portion.

The increase in fog due to pressure is ΔFog.

In an exposure area of 100 times or less of the exposure amount E ₀ which gives a density of fog + 0.2, the density becomes 0.0 due to the pressure between certain exposure amounts E ₁ to E _2.
When decreasing by 1 or more Pressure desensitization area = ((logE ₂ −logE ₁ ) / 2) ×
It is set to 100 (%). The results obtained are shown in Table 1.

[0196]

[Table 1] As is clear from Table 1, according to the present invention, an emulsion having low fog, high sensitivity, pressure fog and pressure desensitization can be obtained. Example 2 (1) Preparation of Emulsion Tabular silver iodobromide core emulsion 2-A was prepared in the same manner as Emulsion 1-A of Example 1 except the following. Keeping the temperature at 30 ° C instead of 60 ° C, 1.9M AgN
O ₃ aqueous solution 8 cc and 1.7 M KBr aqueous solution 9.6 cc
In place of 45 s instead of 48 cc of 0.1 M AgNO ₃ solution and 25 cc of 0.2 M KBr solution.
Added in seconds. Instead of aging in the presence of NH ₃ , N
Physical aging without H ₃ was carried out for 20 minutes. The obtained silver iodobromide grains have an average equivalent circle diameter of 2.5 μm and an average thickness of 0.15 μm.
It was a tabular grain having m and an average aspect ratio of 17.

Tabular silver iodobromide emulsion 2-B was prepared in the same manner as emulsion 1-B except for the following.

Emulsion 2-A was used in place of core emulsion 1-A. The obtained silver iodobromide emulsion has an average equivalent circle diameter of 2.8 μm.
m, average thickness 0.19 μm, and average aspect ratio 15 were tabular grains, and the same was true for the following emulsion 2-C.

Tabular silver iodobromide emulsion 2-C was prepared in the same manner as emulsion 1-H except for the following.

Emulsion 2-A was used in place of core emulsion 1-A. (2) Chemical sensitization For emulsions 1-B, 1-H, 2-B and 2-C, the sensitizing dyes shown in Table 2 were added before chemical sensitization at 7.0 × 10 ⁻⁴ mol / mol Ag. , 1/100 ″ exposure, gold and sulfur were sensitized so that the sensitivity was highest. (3) Preparation of coated sample and its evaluation The coated sample S-11 to S-11 were prepared in the same manner as in Example 1. S-18
Was produced.

The results obtained are shown in Table 2.

[0202]

[Table 2] As is clear from Table 2, the same effects as in Example 1 were observed when the sensitizing dye was added before chemical sensitization and when high aspect ratio tabular grains were used. Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a multilayer color light-sensitive material. (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 point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Samples S-31 to S-35) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 Second layer (intermediate) Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1. 8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-4 0.17 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0. 070 HBS-1 0.060 gelatin 0.87 4th layer ( Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.20 ExC -0.050 ExC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30 5th layer (high Sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.097 ExC- 2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) Cpd-1 0.040 HBS-1 0. 020 Gelatin 0.80 7th layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0. ^{0 ExS-4 2.6 × 10 -5} ExS-5 1.8 × 10 -4 ExS-6 6.9 × 10 -4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY -1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (medium-speed green emulsion layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ^-5 ExS- 5 1.5 × 10 ⁻⁴ ExS-6 5.8 × 10 ⁻⁴ ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50 9th layer (high-sensitivity green sensitive emulsion layer) Emulsion E Silver 1.55 ExS-4 4.6x10 ^-5 ExS-5 1.0x10 ^-4 ExS-6 3.9x ^{10 -4 ExC-1 0.015 ExM-} 1 0.013 ExM-4 0.065 ExM-5 0.019 BS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95 11th layer (Low-sensitivity blue-sensitive emulsion layer) Emulsion (shown in Table 3) Silver 0.40 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.042 ExY-2 0.87 ExC-7 7.0 × 10 ^{− 3} HBS-1 0.30 Gelatin 1.5 12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ⁻⁴ ExY-2 0.20 HBS-1 0.070 Gelatin 0.69 13th layer (first protection layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 14th layer 2 protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, the storability, processability, pressure resistance, and Anti-mildew
To improve antibacterial property, antistatic property and coating property, W-
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained. The emulsions indicated by the above abbreviations are shown in Table 3 below.

[0203]

[Table 3] In Table 3, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope. (5) Emulsions A to G are silver iodobromide.

The compounds used for forming each of the above layers are as follows.

[0205]

[Chemical formula 22]

[0206]

[Chemical formula 23]

[0207]

[Chemical formula 24]

[0208]

[Chemical 25]

[0209]

[Chemical formula 26]

[0210]

[Chemical 27]

[0211]

[Chemical 28]

[0212]

[Chemical 29]

[0213]

[Chemical 30]

[0214]

[Chemical 31]

[0215]

[Chemical 32]

[0216]

[Chemical 33]

[0217]

[Chemical 34] Using the emulsions shown in Table 4 for the 11th layer, Samples S-31 to
S-35 was produced. The emulsion was prepared according to Example 1. However, the octahedral grains of Sample S-35 are the same as those disclosed in JP-A-2-6.
The size was reduced according to the example of No. 8538, and the high iodine layer was shelled according to the example 1 of the present invention. Development was carried out in the same manner as in Example 1 except that the color development time was 3'15 ". The sensitivity was indicated by the relative value of the reciprocal of the exposure amount giving a density of Fog + 1.0.

The sharpness was evaluated by measuring MTF. The MTF was measured by the method described in "Journal of Applied Photographic Engineering" Vol. 6 (1) 1-8 (1980). The MTF value was evaluated as a cyan color image at a spatial frequency of 10 lines / mm, and shown as a relative value.

[0219]

[Table 4] As shown in Table 4, a silver halide photographic light-sensitive material having high sensitivity and excellent pressure characteristics was obtained by using the emulsion of the present invention. Further, by using the tabular emulsion of the present invention, the sharpness of the lower layer can be improved without deteriorating pressure fog and desensitization.

[0220]

According to the present invention, a silver halide photographic light-sensitive material having low fog, high sensitivity, improved pressure resistance and excellent sharpness can be obtained.

(72) Inventor Hiroyuki Kawamoto, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Inventor, Morio Yagihara, 210 Nakanuma, Minami Ashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd.

Claims (7)

[Claims] 1. A silver halide grain is formed while rapidly generating iodide ions, and the silver halide grain is spectrally sensitized with a sensitizing dye represented by the formula (I) shown in the following chemical formula 1. A silver halide photographic emulsion characterized in that [Chemical 1] In formula (I), Z ₁ and Z ₂ together with N and C are 5 to 6
Represents a non-metal atom group forming a member heterocycle, and R ₃ and R
₄ represents an alkyl group, X ₁ ^- represents an anion,
p represents 1 or 2. 2. An iodide ion-releasing agent is used such that 100 to 50% of the iodide ion-releasing agent present in the reaction vessel substantially completes the release of iodide ion within 180 consecutive seconds. The silver halide photographic emulsion according to claim 1. 3. The silver halide photographic emulsion according to claim 1, which is a silver halide grain formed by rapidly generating iodide ions using an iodide ion releasing agent and an iodide ion release controlling agent. 4. A reaction for rapidly generating iodide ions is a second-order reaction substantially proportional to the iodide ion-releasing agent concentration and the iodide ion-releasing regulator concentration, and its second-order reaction rate constant is 1000. To 5 × 10 ^-3 (M ^-1 · sec
^The silver halide photographic emulsion according to claim 1, wherein the iodide ion-releasing agent which is ^-1 ) is used. 5. A silver halide photographic emulsion according to claim 1, wherein iodide ions are rapidly produced from an iodide ion releasing agent represented by the formula (II) shown below. [Chemical 2] In formula (II), R represents a monovalent organic residue that releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. 6. A silver halide photographic emulsion according to claim 1, wherein the silver halide tabular grains having an aspect ratio of 2 to 30 occupy 100 to 50% of the projected area of all the silver halide grains in the emulsion. 7. A photographic light-sensitive material containing the silver halide photographic emulsion according to claim 1.