JPH1010668A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the change of the photographic performance of an emulsion completed at the time of producing a photographic sensitive material with the lapse of time as well as to obtain a photographic sensitive material less liable to the change of the photographic performance even at high temp. and humidity by incorporating specified compds. SOLUTION: This silver halide photographic sensitive material contains a compd. represented by formula I and a compd. represented by formula III. In the formula I, Het is a group adsorbed on silver halide, Q is a divalent combining group consisting of atoms including at least one of C, N, S and O atoms and Hy is a group having a hydrazine structure represented by formula II, wherein each of R11 -R14 is an aliphatic group, aryl or a heterocyclic group, each of k1 and k3 is 1-3 or 4 and k2 is 0 or 1. In the formula III, R61 is an aliphatic group, aryl, acyl, alkyl, arylsulfonyl, etc., and R62 is H or has the same meanings as R61 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material which is excellent in raw preservability and latent image preservability and has high stability to production conditions by containing a specific organic compound.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials,
It is required that the sensitivity be high, and that the fluctuation in photographic properties due to storage after the production of the photosensitive material and the fluctuation in photographic properties due to storage after photographing and until development processing be small.
In recent years, Fuji Photo Film Co., Ltd.'s film with a lens, "Kareru", has become widespread. With the widespread use of such film with a lens, silver halide photosensitive materials are often stored in a higher temperature and higher humidity environment. Photosensitive materials are strongly desired. It is known from JP-A-7-134,351 that addition of a certain compound having a hydrazino group as a substituent to a light-sensitive material can suppress an increase in fog. In the examples in the specification, the fogging concentration was measured without subjecting the prepared sample to particularly high-temperature, high-humidity conditions, and it was shown that the compound did not cause an increase in fogging.
The present inventors have newly found that the compounds described in the specification extremely effectively suppress photographic fluctuation under storage conditions of high temperature and high humidity. Also, Japanese Unexamined Patent Publication No. 7-239,5
No. 40 describes that addition of a certain compound having a hydroxylamino group as a substituent can suppress an increase in fog due to long-term storage. The present inventors have found that the compounds described in the specification also suppress photographic fluctuation under high temperature and high humidity conditions. However, the addition of these compounds has created new problems.

[0003] Emulsions used in photographic light-sensitive materials are not coated on a support immediately after preparation, but are preserved as such for a certain period for various reasons during production. The emulsion in this state is called a completed emulsion. Since the aging time until the coating of the finished emulsion varies from batch to batch, variability in photographic properties due to differences in aging time is a large load on the production of photographic light-sensitive materials, which is not preferable. Although the compound which suppresses the fluctuation of photographic properties under high temperature and high humidity as described above functions effectively in the light-sensitive material, the fog of the finished emulsion may be increased by a change with time in the present invention. It became clear by examination of persons. Although the exact reason why the opposite phenomenon occurs between the light-sensitive material and the finished emulsion is not known at all, it has been strongly desired to suppress the change in photographic properties of the finished emulsion over time.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photographic light-sensitive material having a small photographic fluctuation even under high temperature and high humidity. It is an object of the present invention to provide a photographic light-sensitive material in which a problem in the production of the light-sensitive material, that is, a change in photographic properties of the finished emulsion over time is small.

[0005]

The object of the present invention is to provide (1) at least one compound represented by the following general formula (S1) and at least one compound represented by the following general formula (S2). 1. A silver halide photographic light-sensitive material comprising:

Embedded image In the general formula (S1), Het is an adsorptive group to silver halide. However, the group represented by Het is substituted with at least one-(Q) k2- (Hy). Q represents a divalent linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Hy represents a group having a hydrazine structure represented by the following general formula (II).

Embedded image Wherein (II), R _11, R _12, R ₁₃ and R ₁₄ each represent an aliphatic group, an aryl group or a heterocyclic group, R ₁₁ and R _12, R
₁₃ and R ₁₄ , R ₁₁ and R ₁₃ or R ₁₂ and R ₁₄ may be bonded to each other to form a ring. Provided that at least one of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is represented by-in the general formula (S1).
(Q) _k2- (Het) _k1 is a divalent aliphatic group, aryl group or heterocyclic group to be substituted, k1 and k3 each represent 1, 2, 3 or 4, and k2 represents 0 or 1. Represent

Embedded imageIn the general formula (S2), R₆₁Represents an aliphatic group, an aryl group,
Group, alkyl or arylsulfonyl group, alkyl
Or arylsulfinyl group, carbamoyl group, sulf
Famoyl group, alkoxycarbonyl group or aryl
Represents an oxycarbonyl group;₆₂Is a hydrogen atom or R₆₁
Represents a group having the same meaning as the group shown by. Where R ₆₁Is an aliphatic group
Or an aryl group, R₆₂Is an acyl group, alkyl or
Arylsulfonyl group, alkyl or arylsulf
Ynyl group, carbamoyl group, sulfamoyl group, alcohol
Xycarbonyl group or aryloxycarbonyl group
is there. R₆₁And R₆₂Combine with each other to form a 5- to 7-membered ring
May have been solved by.

The compound represented by the general formula (S2) is a certain compound having a hydroxylamino group as a substituent described in JP-A-7-239,540.
The compound represented by the general formula (S1) is disclosed in JP-A-7-13
No. 4,351. When each of these compounds is added alone, there is a drawback that photographic properties vary with the aging time of the finished emulsion. This is not described in the above-mentioned publication, and the photographic property is suppressed by using the compound represented by the general formula (S1) and the compound represented by the general formula (S2) in combination. It was found for the first time that the inventors could do so. These effects of the present invention will be described in more detail in examples below.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. First, the hydrazine structure represented by the general formula (II) preferably used as Hy will be described in detail. In the formula (II), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄
Represents an aliphatic group, an aryl group or a heterocyclic group. Also,
R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₁ and R ₁₃ , and R ₁₂ and R
₁₄ may combine with each other to form a ring, but do not form an aromatic heterocyclic ring. However, at least one of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is represented by-in the general formula (S1).
(Q) _k2- (Het) _k1 is a divalent aliphatic group, aryl group or heterocyclic group to be substituted. As used herein, the term "aliphatic group" refers to an aliphatic hydrocarbon group which may be linear, branched or cyclic, may contain a saturated or unsaturated bond, may be unsubstituted or may be substituted. And each includes a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, and the like.

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are, for example, unsubstituted aliphatic groups having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, isopropyl) Group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group, cyclopentyl group, cyclopropyl group, cyclohexyl group), a substituted aliphatic group having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. No.

Here, if the substituent is V, the substituent represented by V is not particularly limited, but is, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). Atom), hydroxy group, alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group (for example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), aryloxy Groups (for example, phenoxy group, 4-methylphenoxy group, α-naphthoxy group),
Acyloxy group (eg, acetyloxy group, propionyloxy group), acyl group (eg, acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, Peridinocarbonyl group), sulfamoyl group (for example, sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl group (eg, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group), heterocyclic group (eg, A 2-pyridyl group, a tetrahydrofurfuryl group, a morpholino group,
2-thienyl group), amino group (for example, amino group, dimethylamino group, anilino group, diphenylamino group), alkylthio group (for example, methylthio group, ethylthio group),
Alkylsulfonyl group (for example, methylsulfonyl group,
Propylsulfonyl group), alkylsulfinyl group (eg, methylsulfinyl group), nitro group, phosphate group, acylamino group (eg, acetylamino group), ammonium group (eg, trimethylammonium group, tributylammonium group), hydrazino group (eg, trimethylhydra) Diino group), ureido group (for example, ureido group, N, N-
Dimethylureido group), imide group, unsaturated hydrocarbon group (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group), aryl group (for example, phenyl group, naphthyl group), heterocyclic group ( For example, a pyridyl group). Substituent V has 1 carbon atom
To 18 are preferable, and 1 to 8 are more preferable. V may be further substituted on these substituents.

More specifically, an aliphatic group (for example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl Group,
3-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-cyanoethyl group, 2-chloroethyl group,
-Bromoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-ethoxycarbonylethyl group, methoxycarbonylmethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-phenoxyethyl group, 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2-acetylethyl group, 3-benzoylpropyl group, 2-carbamoylethyl group, 2-morpholinocarbonylethyl group, sulfamoylmethyl group, 2- (N, N-dimethylsulfamoyl) ethyl group, benzyl group, 2-naphthylethyl group, 2- (2-pyridyl) ethyl group, allyl group,
3-aminopropyl group, 3-ditylaminopropyl group,
Methylthiomethyl group, 2-methylsulfonylethyl group,
Methylsulfinylmethyl group, 2-acetylaminoethyl group, 3-trimethylammoniumethyl group, 2-mercaptoethyl group, 2-trimethylhydrazinoethyl group,
A methylsulfonylcarbamoylmethyl group, a (2-methoxy) ethoxymethyl group, etc., and an aryl group having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms (for example, phenyl group, α-naphthyl group, β-naphthyl) A phenyl group or a naphthyl group substituted with the aforementioned substituent V or an aliphatic group), and having 4 to 1 carbon atoms.
8, more preferably 4 to 12 heterocyclic groups (for example, 2-
A pyridyl group, a 2-pyridyl group substituted with the aforementioned substituent V or an aliphatic group).

Further, R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₁ and R 12
₁₃ , and R ₁₂ and R ₁₄ may combine with each other to form a ring. However, it does not form an aromatic heterocycle. These rings may be substituted, for example, by the substituent V described above.

R₁₁, R₁₂, R₁₃And R₁₄As further
Preferably, an unsubstituted aliphatic group, a substituted aliphatic group, and R
₁₁And R₁₂, R₁₃And R₁₄, R₁₁And R₁₃, And R₁₂, R₁₄
Are bonded to each other to form a ring other than a carbon atom
Does not contain (eg, oxygen, sulfur, nitrogen)
Alkylene group ｛alkylene group is substituted (for example,
Group V), which may be｝.
R₁₁, R₁₂, R₁₃And R₁₄More preferably,
The carbon atom directly bonded to the hydrazine nitrogen atom is
This is the case of an unsubstituted methylene group. R₁₁, R₁₂, R₁₃, R
₁₄Is particularly preferably an unsubstituted alkyl having 1 to 6 carbon atoms.
Kill groups (e.g., methyl, ethyl, propyl,
Tyl group), a substituted alkyl group having 1 to 8 carbon atoms {eg,
Sulfoalkyl group (for example, 2-sulfoethyl group, 3-s
Rufopropyl group, 4-sulfobutyl group, 3-sulfobuty
Carboxyalkyl group (eg, carboxymethyl group)
Group, 2-carboxyethyl group), hydroxyalkyl
Groups (eg, 2-hydroxyethyl groups)} and R₁₁And R
₁₂, R₁₃And R₁₄, R₁₁And R ₁₃, And R₁₂And R₁₄Is al
A 5-membered ring, a 6-membered ring and
This is the case where a 7-membered ring is formed. Represented by the general formula (II)
At least one-(Q)_k2−
(Het)_k1 Has been replaced. The substitution position is R₁₁,
R₁₂, R₁₃And R₁₄Either may be used.

The hydrazine compound represented by the general formula (II) may be isolated as a salt at any time when it is advantageous in synthesis and storage. In such a case, any compound may be used as long as it can form a salt with hydrazines. For example, aryl sulfonates (e.g., p-toluenesulfonate, p-chlorobenzenesulfonate), aryldisulfonates (e.g., 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonic acid, 2,2) 6-naphthalenedisulfonate), thiocyanate, picrate, carboxylate (eg, oxalate, acetate, benzoate, hydrogen oxalate), halogenate (eg, hydrochloride, fluoride) Hydrochloride, hydrobromide, hydroiodide), sulfate, perchlorate, tetrafluoroborate, sulfite, nitrate, phosphate, carbonate, bicarbonate. Preferred are hydrogen oxalate, oxalate and hydrochloride.

Further, the compound represented by the general formula (II) of the present invention is particularly preferable when it is a compound selected from the following general formulas (III), (IV) and (V).

[0015]

Embedded image

In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent an aliphatic group, an aryl group or a heterocyclic group. Also, R ₁₅
And R ₁₆ and R ₁₇ and R ₁₈ may be bonded to each other to form a ring. Z ₁₁ represents an alkylene group having 4, 5 or 6 carbon atoms. Z ₁₂ represents an alkylene group having 2 carbon atoms. Z ₁₃ represents an alkylene group having 1 or 2 carbon atoms. Z ₁₄ and Z ₁₅ represent an alkylene group having 3 carbon atoms. L ₁₁ and L ₁₂ represent a methine group. In general formulas (III), (IV) and (V), at least one _of- (Q) _k2- (Het) _k1 is substituted.
More preferred are compounds selected from the general formulas (III) and (IV), and particularly preferred are compounds selected from the general formula (III).

Hereinafter, the general formula (III) will be described in detail. R ₁₅ and R ₁₆ have the same meanings as R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ , and the preferred range is also the same. Particularly preferred is the case where the alkyl group and R ₁₅ and R ₁₆ are bonded to each other to form an unsubstituted tetramethylene group or pentamethylene group. Z ₁₁ represents an alkylene group having 4, 5 or 6 carbon atoms, preferably an alkylene group having 4 or 5 carbon atoms. However, the oxo group is not substituted on the carbon atom directly bonded to the nitrogen atom of hydrazine. This alkylene group may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and it is preferable that the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. Z ₁₁ is particularly preferably an unsubstituted tetramethylene group or an unsubstituted pentamethylene group. General formula (III)
At least one hydrazine group represented by-
(Q) _k2- (Het) _k1 is substituted. The substitution position may be any of R ₁₅ , R ₁₆ and Z ₁₁ . Preferably, they are R ₁₅ and R ₁₆ .

Hereinafter, the general formula (IV) will be described in detail. R ₁₇ and R ₁₈ have the same meanings as R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ , and the preferred ranges are also the same. Particularly preferred is the case where the alkyl group and R ₁₇ and R ₁₈ are bonded to each other to form a trimethylene group. Z ₁₂ has 2 carbon atoms
Represents an alkylene group. Z ₁₃ has 1 or 2 carbon atoms
Represents an alkylene group. These alkylene groups may be unsubstituted or substituted. As the substituent,
For example, the aforementioned substituent V can be mentioned. More preferably, Z ₁₂ is an unsubstituted ethylene group. Z ₁₃ is more preferably an unsubstituted methylene group or an ethylene group. L ₁₁ and L ₁₂ represent a substituted or unsubstituted methine group. Examples of the substituent include the substituent V described above, and preferably an unsubstituted alkyl group (for example, a methyl group, t
-Butyl group). More preferably, it is an unsubstituted methine group. The hydrazine group represented by the general formula (IV) is substituted by at least one _of- (Q) _k2- (Het) _k1 . The substitution position may be any of R ₁₇ , R ₁₈ , Z ₁₂ , Z ₁₃ , L ₁₁ and L ₁₂ . Preferably from R ₁₇ and R _18.

The general formula (V) will be described in detail. Z
₁₄ and Z ₁₅ represent an alkylene group having 3 carbon atoms.
However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group. Z ₁₄ and Z ₁₅
Particularly preferred are an unsubstituted trimethylene group, an unsubstituted alkyl group and a substituted trimethylene group (for example, a 2,2-dimethyltrimethylene group). The hydrazine group represented by the general formula (V) has at least _one- (Q) _k2- (He
t) _k1 is substituted. The substitution positions are Z ₁₄ and Z ₁₅
Either may be used. The compounds represented by the general formulas (III), (IV) and (V) may be isolated as salts similarly to the compounds represented by the general formula (II). Examples of the salt include those similar to the salt represented by the general formula (II). Preferred are hydrogen oxalate, oxalate and hydrochloride.

Next, the group represented by Het in formula (S1) will be described in detail. Het is an adsorptive group to silver halide. Preferably, Het is a group having a 5-, 6- or 7-membered heterocycle containing at least one heteroatom. More preferably, Het is:
Having the structure of any of 5, 6, or 7-membered nitrogen-containing heterocycle having a quaternary nitrogen atom represented by the following A, 5, 6, or 7 represented by the following B having a thioxo group
Membered nitrogen-containing heterocycle 5, 6 or 7-membered nitrogen-containing heterocycle represented by C below 5, 6, or 7-membered nitrogen-containing heterocycle represented by D or E below Mesoion represented by F below

[0021]

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The heterocyclic ring represented by A is a 5-, 6-, or 7-membered
Membered nitrogen-containing heterocyclic ring, examples of the atoms constituting the ring include, for example, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and preferably an imidazolium ring, a pyrazolium ring, and an oxazolium Ring, isoxazolium ring, thiazolium ring, isothiazolium ring, 1,3,4-oxadiazolium ring, 1,2,3
-Triazolium ring, 1,2,4-thiadiazolium ring, 1,2,3,4-oxatriazolium ring, 1,
Examples include a 2,3,4-tetrazolium ring and a 1,2,3,4-thiatetrazolium ring. Ra is preferably the same as the above-mentioned examples of the aliphatic group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ . The heterocycle represented by BE is a 5-, 6- or 7-membered heterocycle containing at least one heteroatom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom); Preferably an azole ring (eg imidazole, triazole, tetrazole, oxazole, selenazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, thiadiazole, oxadiazole,
Benzoselenazole, pyrazole, naphthothiazole,
Naphthoimidazole, naphthoxazole, azabenzimidazole, purine), pyrimidine ring, triazine ring, azaindene ring (for example, triazaindene, tetrazaindene, pentaazaindene) and the like.

The meso ion represented by F is W. Bake
r and WDOllis Quarterly Review
v.) 11 pages 15 (1957), Advances in Heterocyclic Chemistry (Advances in He
Terocyclic Chemistry), vol. 19, p. 1 (1976), which states that “a 5- or 6-membered heterocyclic compound cannot be satisfactorily represented by one covalent structural formula or polar structural formula. And compounds having a pi-electron hexaploid associated with all the atoms that make up the ring, the ring bears a partial positive charge and remains balanced with an equal negative charge on the exocyclic atom or group. " Represents

The heterocyclic ring represented by F is a 5- or 6-membered heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and is preferably an imidazolium, a pyrazolium, an oxazolium. , Isoxazolium, thiazolium, isothiazolium, 1,3-dithiol, 1,3,4-oxadiazolium, 1,2,3-oxadiazolium, 1,
3,2-oxathiazolium, 1,2,3-triazolium, 1,3,4-triazolium, 1,2,3
-Thiadiazolium, 1,2,4-thiadiazolium, 1,2,3,4-oxatriazolium, 1,
Examples thereof include 2,3,4-tetrazolium and 1,2,3,4-thiatetrazolium. R ₁₀ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group;
_{The following} are examples of _eleven . However, the group represented by Het includes at least one-(Q)
_k2- (Hy) is substituted. More preferred as Het are the following general formulas (VI), (VII), (VIII),
Compounds represented by (IX), (X) and (XI).

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom or a monovalent substituent. R ₃₄ ,
R ₃₁ , R ₃₂ and R ₃₃ represent an aliphatic group, an aryl group or a heterocyclic group. X ₁₁ represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. Y ₁₁ is an oxygen atom, a sulfur atom, ＝ NH, ＮN- (L ₁₄ ) _p3 —R ₃₈ , L ₁₃ and L ₁₄ represent a divalent linking group, and R ₃₅ and R ₃₈ are a hydrogen atom, a fat Represents a group, an aryl group or a heterocyclic group. X ₁₂ has the same meaning as X _11. p ₂ and p ₃ 0-3
Is an integer. Z ₁₇ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₃₆ represents an aliphatic group. R ₃₇ represents a hydrogen atom or an aliphatic group. However, each of the general formulas (VI) to (XI) has at least 1
-(Q) _k2- (Hy) are substituted. However, X ₁₁ and X ₁₂ in formulas (VIII) and (IX) are not substituted. Among the general formulas (VI) to (XI), the general formulas (VI), (VIII), (IX) and (XI) are preferable, and the general formula (VIII) is more preferable.

Next, general formulas (VI), (VII), (VIII),
(IX), (X) and (XI) will be described in more detail. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the substituents described above as preferred examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and V. More preferably, a lower alkyl group (preferably substituted or unsubstituted one having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, methoxy group) Ethyl group, hydroxyethyl group, hydroxymethyl group, vinyl group, allyl group), carboxy group, alkoxy group (preferably substituted or unsubstituted one having 1 to 5 carbon atoms, for example, methoxy group, ethoxy group, methoxyethoxy group , Hydroxyethoxy group),
An aralkyl group (preferably substituted or unsubstituted
12 groups such as benzyl group, phenethyl group and phenylpropyl group, and aryl group (preferably substituted or unsubstituted group having 6 to 12 carbon atoms such as phenyl group,
4-methylphenyl group, 4-methoxyphenyl group), heterocyclic group (for example, 2-pyridyl group), alkylthio group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, for example, methylthio group, ethylthio group), Arylthio group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms such as phenylthio group), aryloxy group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms such as phenoxy group), number of carbon atoms Three or more alkylamino groups (eg, propylamino group, butylamino group), arylamino groups (eg, anilino group), halogen atoms (eg, chlorine atom, bromine atom, fluorine atom), or the following substituents .

[0033]

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Here, L ₁₅ , L ₁₆ and L ₁₇ each represent a linking group represented by an alkylene group (preferably having 1 to 5 carbon atoms, for example, a methylene group, a propylene group or a 2-hydroxytrimethylene group). . R ₃₉ and R ₄₀ may be the same or different, and each represents a hydrogen atom, an aliphatic group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, t-butyl group, n-octyl group, methoxyethyl group, hydroxyethyl group, allyl group, propargyl group), aralkyl group (preferably substituted or unsubstituted one having 7 to 12 carbon atoms) For example, a benzyl group, a phenethyl group, a vinylbenzyl group), an aryl group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms, for example, a phenyl group or a 4-methylphenyl group), or a heterocyclic group (for example, 2 -Pyridyl group).

The aliphatic group, aryl group and heterocyclic group represented by R ₃₄ , R ₃₁ , R ₃₂ and R ₃₃ may be unsubstituted or substituted. Preferably, the substituents exemplified as R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and V can be exemplified. More preferably, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), nitro group, cyano group, hydroxy group, alkoxy group (eg, methoxy group), aryl group (eg, phenyl group), acylamino group (eg, propionylamino group) ), An alkoxycarbonylamino group (for example, a methoxycarbonylamino group), an ureido group, an amino group, a heterocyclic group (for example, a 2-pyridyl group), an acyl group (for example, an acetyl group), a sulfamoyl group, a sulfonamide group, a thioureido group, and carbamoyl. Groups, alkylthio groups (eg, methylthio groups), arylthio groups (eg, phenylthio groups, heterocyclic thio groups (eg, 2-benzothiazolylthio groups), carboxylic acid groups, sulfonic acid groups, and salts thereof. The above ureido group, thioureido group, Rufamoiru group, those carbamoyl group, each amino group unsubstituted those N- alkyl-substituted, N
-Including aryl substituted. Examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent include the substituents described above as preferred examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and V.

The alkali metal atoms represented by X ₁₁ and X ₁₂ are, for example, a sodium atom and a potassium atom, and the ammonium groups are, for example, tetramethylammonium and trimethylbenzylammonium. The precursor is a group that can become a hydrogen atom, an alkali metal or ammonium under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, and a methanesulfonylethyl group. Specific examples of the divalent linking group represented by L ₁₃ and L ₁₄ include the following linking groups or a combination thereof.

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R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R
_47, R _48, R ₄₉ and R ₅₀ represents a hydrogen atom, an aliphatic group (preferably having from 1 to 4 carbon atoms, a substituted or unsubstituted, e.g., methyl group, ethyl group, n- butyl group, methoxyethyl Group, hydroxyethyl group, allyl group) or aralkyl group (preferably substituted or unsubstituted C 7 -C 12)
Benzyl group, phenethyl group, phenylpropyl group).

R ₃₅ and R ₃₈ are preferably the same as those described above for R ₃₄ . Preferred as Z ₁₇ are thiazoliums such as thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, Methylbenzothiazolium,
6-methoxybenzothiazolium, naphtho [1,2-
d] thiazolium, naphtho [2,1-d] thiazolium}, oxazolium {eg oxazolium, 4-
Methyl oxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium, imidazoliums, for example 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-
5,6-cyclobenzimidazolium, 1-allyl-
5-trifluoromethyl-6-chloro-benzimidazolium), selenazoliums {e.g., benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [ 1,2-d] selenazolium} and the like. Particularly preferred are thiazoliums (for example, benzothiazolium, 5-chlorobenzothiazolium,
Methoxybenzothiazolium and naphtho [1,2-d] thiazolium).

R ₃₆ and R ₃₇ are preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl,
Decyl, dodecyl, octadecyl), or a substituted alkyl group as a substituent, for example, a vinyl group, a carboxy group,
Sulfo group, cyano group, halogen atom (for example, fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group having 1 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), carbon number 1 to 8 alkoxy groups (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), 6 to 10 carbon atoms of a monocyclic aryloxy group (for example, phenoxy, p-tolyloxy), 1 to 1 carbon atoms
3 acyloxy groups (eg, acetyloxy, propionyloxy), C 1-8 acyl groups (eg, acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidi) Carbonyl), a sulfamoyl group (eg, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl,
Piperidinosulfonyl), and an alkyl group having 1 to 18 carbon atoms で substituted with an aryl group having 6 to 10 carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl). However, R ₃₆ is not a hydrogen atom. More preferably, R ₃₆ is an unsubstituted alkyl group (eg, methyl, ethyl) or alkenyl group (eg, allyl group), and R ₃₇ is a hydrogen atom and an unsubstituted lower alkyl group (eg, methyl, ethyl).

When M ₁ and m ₁ are required to neutralize the ionic charge of the compound represented by the general formula (X),
Included in the formula to indicate the presence or absence of a cation or anion. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be specifically an inorganic or organic anion, such as a halogen anion (eg, a fluoride ion, Chlorine ion, bromide ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion), 1 2,5-naphthalenedisulfonic acid imide, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, Acetate ion, trifluorometa Sulfonate ion. Preferably, they are an ammonium ion, an iodine ion, a bromine ion, and a p-toluenesulfonic acid ion.

Nitrogen-containing compounds represented by the general formulas (VI) to (XI)
Each heterocycle has at least one-(Q)_k2−
(Hy) is substituted. The substitution position is R_{twenty one},
R_{twenty two}, R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, R₃₄, R₃₅, R₃₆, R
₃₁, R₃₂, R₃₃Y₁₁, L₁₃And Z ₁₇And so on.

In the general formula (S1), Q is a carbon atom,
It represents a divalent linking group consisting of an atom or an atomic group containing at least one of a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group having 1 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group), an arylene group having 6 to 12 carbon atoms (for example, phenylene group, naphthylene group), carbon number Two
8 alkenylene groups (e.g., ethynylene groups, propenylene groups), amide groups, ester groups, sulfonamide groups, sulfonic acid ester groups, ureido groups, sulfonyl groups, sulfinyl groups, thioether groups, ether groups, carbonyl groups, -N (R ₀ )-(R ₀ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), a heterocyclic divalent group (for example, 6-chloro-1,
3,5-triazine-2,4-diyl group, pyrimidine-
2,4-diyl group, quinoxaline-2,3-diyl group)
Having 4 to 2 carbon atoms formed by combining one or more of
Represents a divalent linking group of 0. More preferred are ureido, ester and amide groups.

K1 and k3 are preferably 1 or 2. More preferably, k1, k2 and k3 are all 1
Is the case. When k1 or k3 is 2 or more, Hy, H
et may be the same or different.

Among the compounds represented by formula (S1) of the present invention, more preferred compounds are those represented by the following formulas (XII) to (XII).
(XVII).

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Further, a particularly preferred compound of the present invention is represented by the following formula (XVIII). General formula (XVIII)

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In the formula, Qa has the same meaning as Q. Zb is Z ₁₁
Is synonymous with R ₅₁ represents a monovalent substituent. R ₅₂ represents an aliphatic group, an aryl group or a heterocyclic group. R ₅₃ and R
₅₄ represents a hydrogen atom or a monovalent substituent. n ₁ is 0-4
Represents an integer. n ₂ represents 0 or 1. n ₃ is 1
Represents an integer of up to 6. When n ₁ and n ₃ are 2 or more,
R ₅₁ and C (R ₅₃ ) (R ₅₄ ) are repeated but need not be the same.

More specifically, Qa is preferably the same as Q, more preferably a ureido group, an ester group or an amide group. Zb is preferably the same as Z _11, more preferably an unsubstituted tetramethylene group, a pentamethylene group. R ₅₁ is preferably the same as R ₂₁ . R ₅₂ is preferably the same as R ₁₁ , R ₁₂ , R ₁₃ and R _14, and is particularly preferably an unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl and ethyl). R ₅₃ and R
₅₄ is preferably the same as R _21, particularly preferably a hydrogen atom. n ₁ is preferably 0. n ₂ is preferably 1. n ₃ is preferably an integer of 2 to 4.

Next, typical examples of the compound represented by the general formula (S1) are shown below, but it should not be construed that the invention is limited thereto.

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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He of the general formula (S1) used in the present invention
t is U.S. Pat. No. 3,266,897, Belgian Patent No. 671,402, JP-A-60-138548, JP-A-59-68732, JP-A-59-123838.
No., JP-B-58-9939, and JP-A-59-13795.
No. 1, JP-A-57-202531, JP-A-57-16
No. 4734, JP-A-57-14836, JP-A-57-14836.
No. 116340, U.S. Pat. No. 4,418,140, JP-A-58-95728, JP-A-55-79436,
OLS 2,205,029, OLS 1,962,60
5, JP-A-55-59463, JP-B-48-182.
No. 57, JP-B-53-28084, JP-A-53-48
No. 723, JP-B-59-52414, JP-A-58-2
No. 17928, JP-B-49-8334, U.S. Patent No. 3,598,602, U.S. Patent No. 887,009,
UK Patent 965,047, Belgium Patent 7378
09, U.S. Pat. No. 3,622,340,
-87322, JP-A-57-211142, JP-A-58-158631, JP-A-59-15240, U.S. Pat. No. 3,671,255, JP-B-48-34166.
No., JP-B-48-322112, JP-A-58-221
No. 839, JP-B-48-32367, JP-A-60-1
No. 30731, JP-A-60-122936, JP-A-6-122
No. 0-117240, U.S. Pat. No. 3,228,770,
JP-B-43-13496, JP-B-43-10256
No., JP-B-47-8725, JP-B-47-30206
No., JP-B-47-4417, JP-B-51-25340
No. 1,165,075, U.S. Pat.
No. 2,982, U.S. Pat. No. 1,472,845, JP-B-39-22067, JP-B-39-22068, U.S. Pat. No. 3,148,067, U.S. Pat.
No. 1, U.S. Pat. No. 3,909,268, JP-B-50-4
No. 0665, Japanese Patent Publication No. 39-2829, U.S. Pat.
48,066, JP-B-45-22190, U.S. Pat. No. 1,399,449, British Patent 1,287,284
No. 3,900,321, U.S. Pat.
5,391, U.S. Patent 3,910,792, British Patent 1,064,805, U.S. Patent 3,544,336
No. 4,003,746; British Patent 1,34
No. 4,525, British Patent No. 972,211, Japanese Patent Publication No. 43
-4136, U.S. Patent 3,140,178, French Patent 2,015,456, U.S. Patent 3,114,637
No., Belgian Patent No. 681,359, U.S. Pat. No. 3,22
0,839, British Patent 1,290,868, US Patent 3,137,578, US Patent 3,420,670
No. 2,759,908; U.S. Pat.
2,340, OLS2,501,261, DAS
No. 1,772,424, U.S. Pat. No. 3,157,509
No. 1, French Patent 1,351,234, US Patent 3,63
0,745, French Patent 2,005,204, German Patent 1,447,796, US Patent 3,915,710
No. JP-B-49-8334, British Patent 1,021,1
No. 99, UK Patent 919,061, Japanese Patent Publication No. 46-17
No. 513, U.S. Pat. No. 3,202,512, OLS2.
553,127, JP-A-50-104927, French Patent 1,467,510, U.S. Pat.
No. 6, US Pat. No. 3,503,936, US Pat.
No. 76,638, French patent 2,093,209, British patent 1,246,311, U.S. Pat.
No. 8, US Pat. No. 3,535,115, British Patent 1,1
No. 61,264, U.S. Pat. No. 3,841,878, U.S. Pat. No. 3,615,616, JP-A-48-39039.
No., UK Patent 1,249,077, JP-B-48-34
No. 166, US Pat. No. 3,671,255, British Patent 1
No. 459160, JP-A-50-6323, British Patent 1,402,819, OLS 2,031,314,
Research Disclosure 13651, U.S. Pat. No. 3,910,791, U.S. Pat. No. 3,954,478
No. 3,813,249; British Patent 1,38
7,654, JP-A-57-135945, JP-A-5-135
7-96331, JP-A-57-22234, JP-A-59-26731, OLS 2,217,153, British Patent 1,394,371, British Patent 1,308,7
77, British Patent 1,389,089, British Patent 1,
No. 347,544, German Patent 1,107,508, U.S. Pat. No. 3,386,831, British Patent 1,129,6
No. 23, JP-A-49-14120, JP-B-46-34
675, JP-A-50-43923, U.S. Pat.
42,481; British Patent 1,269,268; U.S. Patent 3,128,185; U.S. Patent 3,295,98.
No. 1, US Pat. No. 3,396,023, US Pat.
No. 95,827, JP-B-48-38418, JP-A-Showa 4
8-47335, JP-A-50-87028, U.S. Pat. No. 3,236,652, U.S. Pat. No. 3,443,951
No., UK Patent 1,065,669, US Patent 3,31
2,552, U.S. Patent 3,310,405, U.S. Patent 3,300,312, British Patent 952,162,
UK Patent 952,162, UK Patent 948,442
No., JP-A-49-120628, JP-B-48-353
No. 72, JP-B-47-5315, and JP-A-4-143.
No. 756, JP-B-39-18706, JP-B-43-4
No. 941, JP-A-59-34530, etc., and can be synthesized with reference to these.

Hy in the general formula (I) of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Alkylation methods include substitution alkylation using alkyl halide and alkyl sulfonate, reductive alkylation using carbonyl compound and sodium cyanoborohydride, and hydrogenation after acylation. A reduction method using lithium aluminum and the like are known. For example, SRSandle
r), W. Karo, "Organic Functional Group Preparations (Orga
nic Fanctional Group Preparation) ", Volume 1, 14
Chapter, pages 434-465 (1968), Academic Press (Ac
ademic Press), ELClen
nan) etc.Journal of the American Chemical
Society (Journal of The American Chemical S
etc., Vol. 112, No. 13, page 5080 (1990), etc., and can be synthesized by referring to them.

For the bond formation reaction including the amide bond formation reaction and ester bond formation reaction of the-(Q) _k2- (Hy) moiety, a method known in organic chemistry can be used. That is, a method of linking Het and Hy, a method of linking He to a Het synthesis raw material and an intermediate, and then synthesizing Het, and conversely, a method of linking the Hy synthesis raw material and an intermediate to the Het portion, and then synthesizing Hy. Any method such as a method may be used, and it can be appropriately selected and synthesized. For the synthesis reactions for these linkages,
For example, The Chemical Society of Japan, New Experimental Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds, Volume IV, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reaction Theory, Maruzen, Tokyo (1962) LFFieser and
You can refer to books on many organic synthesis reactions such as M. Fieser, Advanced Organic Chemistry, Maruzen, Tokyo (1962). More specifically, JP-A-7-17-1
No. 34,351 can be synthesized by the method shown in Examples 1-2.

(Synthesis Example) The synthesis method of the compound (S1-52) used in the present invention is shown below. The synthetic route is shown in Scheme 1.

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Synthesis of (S1-52B) 300 ml of ethanol was stirred under ice-cooling, and carbon disulfide 40
g was added dropwise. Then, (S1-52A) 75 g (0.5
Mol) was added. 28 g of potassium hydroxide (0.5 g
(Mol) in 300 ml of ethanol was added dropwise over 1 hour under ice-cooling and stirring. Thereafter, the mixture was stirred at room temperature for 1 hour, and the precipitated crystals were collected by filtration. Water 90 is added to the obtained crystals.
0 ml was added and dissolved, and under stirring 140 g of lead nitrate was added to 300 ml of water.
The solution dissolved in was added dropwise. This was heated and stirred in a hot water bath (around 90 ° C.) for 3 hours, cooled, and the precipitate was separated by filtration. The precipitate was washed three times with 500 ml of acetone, and the filtrate and the washing were combined and the solvent was distilled off under reduced pressure. The residue was recrystallized from acetonitrile to obtain 30 g of (S1-52B). Synthesis of (S1-52C) 16 g (0.083 mol) of (S1-52B)
0 ml, ethanol 40 ml, sodium azide 6.5 g
(0.1 mol), and the mixture was heated and refluxed and stirred on a hot water bath for 2 hours. After cooling, the pH was adjusted to about 2 with 6N hydrochloric acid, and the precipitated crystals were collected by filtration to obtain 14 g of (S1-52C). Synthesis of (S1-52D) To 9 g of (S1-52C), 50 ml of a 10% aqueous sodium hydroxide solution was added, and the mixture was heated and stirred under reflux for 2 hours on a hot water bath. Thereafter, the mixture was cooled and acidified by adding concentrated hydrochloric acid, and water was distilled off under reduced pressure. Crystals were precipitated before drying, and the crystals were collected by filtration to obtain 9 g of (S1-52D).

Synthesis of (S1-52F) Methanol (2) was added to 82 ml (1.7 mol) of (S1-52E).
Add 20 ml and dissolve, cool to around -10 ° C and add acetic anhydride.
65 ml (1.7 mol) were added dropwise. During this time, the reaction system
The temperature was adjusted not to exceed ℃. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and then the solvent was distilled off under reduced pressure. 300 ml of methylene chloride was added to the residue, and then a solution of 73 g of sodium hydroxide in 130 ml of water was added dropwise. After obtaining a methylene chloride layer, the aqueous layer was extracted with methylene chloride (300 ml).
× 3), after drying the sodium sulfate, the solvent was distilled off under reduced pressure, and (S1-5)
2F) 100 g were obtained. Synthesis of (S1-52G) N, N was added to 164 g (1.86 mol) of (S1-52F).
-410 ml of dimethylacetamide and 469 g (5.58 mol) of sodium hydrogen carbonate were added,
-402 g (1.86 mol) of dibromobutane were added dropwise over 40 minutes. After stirring for 5 hours, the mixture was filtered and the residue was washed with ethanol. The filtrate and the washing were combined, and the solvent was distilled off under reduced pressure. Ethyl acetate was added to the residue, and after washing with water and saturated saline, ethyl acetate was distilled off under reduced pressure. The residue was purified by column chromatography, and (S1-
52G) 61.3 g were obtained. Synthesis of (S1-52H) 111 ml of concentrated hydrochloric acid was added to 55.5 g (0.39 mol) of (S1-52G), and the mixture was heated and stirred under reflux for 5 hours. Thereafter, concentrated hydrochloric acid was distilled off under reduced pressure to obtain 54.1 g of a residue containing (S1-52H). Synthesis of (S1-52J) To 13.0 g (0.095 mol) of (S1-52H), 65 ml of methanol was added and dissolved, and sodium hydrogencarbonate 8.0 was dissolved.
g (0.095 mol) was added. Next, 32 ml (0.36 mol) of methyl acrylate was added, and the mixture was stirred at room temperature for 24 hours. Thereafter, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography.
J) 9.5 g were obtained. Synthesis of (S1-52K) (S1-52J) 9.5 g of methanol 76 ml, water 28
Then, 18.4 ml of a 28% sodium methoxide methanol solution was added dropwise with stirring at room temperature. After stirring for 4 hours as it was, 7.6 ml of concentrated hydrochloric acid and ethanol were added. After filtering off the insoluble matter, the solvent was distilled off from the filtrate under reduced pressure. Acetonitrile was added to the residue, the insolubles were filtered off, and the solvent was distilled off from the filtrate under reduced pressure to obtain 8.6 g of (S1-52K). Synthesis of (S1-52) N, N was added to 6.1 g (0.026 mol) of (S1-52D).
-Dimethylacetamide (50 ml) was added and dissolved, and potassium t-butoxide (3.0 g, 0.026 mol),
52k) 5.0 g (0.029 mol) was added, and N, N'-diisopropylcarbodiimide (4.1 ml) was stirred at room temperature.
(0.026 mol) was added dropwise. After stirring was continued for 24 hours as it was, the mixture was poured into water, the precipitate was separated by filtration, and the solvent was distilled off from the filtrate under reduced pressure. The residue was purified by silica gel column chromatography and recrystallized from methanol to give (S1-5
2) 2.6 g were obtained. ¹ H-NMR (200 MHz, D
_{MSO-d 6) δ1.7~2.0 (m} , 4H), 2.6
-2.8 (m, 5H), 3.1-3.3 (m, 6H)
7.43 (t, 1H), 7.6 to 7.8 (m, 2H),
8.19 (s, 1H), 10.27 (s, 1H). Melting point 171 [deg.] C-(decomposition). In the present invention, it is preferable to use a spectral sensitizing dye. For example, any dyes such as conventionally known cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, hemicyanine dyes, benzylidene dyes, xanthene dyes, and styryl dyes can be used. For example, "The Theory of the Phot" by THJames
ographic Process) "(3rd edition), pp. 198-228 (1966)
) And dyes described in Macmillan. More preferred are the dyes represented by formulas (XI), (XII) and (XIII) described in JP-A-5-216152, and the dyes described as specific examples are particularly preferred. Particularly preferred are oxacarbocyanine dyes.

In order to incorporate the compound represented by formula (S1) of the present invention and the sensitizing dye to be used in a silver halide emulsion, they may be directly dispersed in the emulsion, or may be dispersed in water or methanol. , Ethanol, propanol, acetone, methylcellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, -Methoxy-2-propanol, N, N-dimethylformamide or the like may be added to the emulsion by dissolving in a solvent alone or in a mixed solvent.

As described in US Pat. No. 3,469,987, a dye or the like is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid.
A method of adding this dispersion to an emulsion, JP-B-46-24
No. 185, etc., a method of dispersing a water-insoluble dye or the like in a water-soluble solvent without dissolving and adding this dispersion to an emulsion, JP-B-44-23389, JP-B-44-27555. As described in JP-B-57-22091, a method of dissolving a dye in an acid and adding the solution to an emulsion or adding an acid or a base to form an aqueous solution in the presence of an acid or a base and adding the resulting solution to an emulsion. 3,822,135
And a method in which an aqueous solution or a colloidal dispersion in the presence of a surfactant is added to an emulsion as described in US Pat. No. 4,006,026.
JP-A-102733, JP-A-58-105141, a method of directly dispersing a dye or the like in a hydrophilic colloid and adding the dispersion to an emulsion.
As described in No. 74624, a method of dissolving a dye using a compound to be redox and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye or the compound represented by the general formula (S)
The compound represented by the formula (1) may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been recognized to be useful. For example, US Pat. No. 2,735,766, US Pat.
No. 8,960, U.S. Pat. No. 4,183,756, U.S. Pat. No. 4,225,666, JP-A-58-184142.
As disclosed in the specification of JP-A No. 60-196749, chemical ripening is carried out during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Before the start of coating, as disclosed in the specification of JP-A-58-113920, etc., immediately before or during the process of chemical ripening, and before the coating of the emulsion after the coating. Then, they may be added at any time in the process. Further, as disclosed in specifications such as U.S. Pat. No. 4,225,666 and JP-A-58-7629,
The same compound may be used alone or in combination with a compound having a heterogeneous structure. The compound to be divided and added may be added in different types or the combination of the compounds may be changed.

The amount of the sensitizing dye used in the present invention depends on the shape and size of the silver halide grains.
Preferably 4 × 10 ^-8 to 8 × per mole of silver halide
It can be used in 10 ^-2 moles. The general formula (S
The compound represented by the formula (1) may be added at any time before or after the sensitizing dye, and the amount of the compound represented by the general formula (S1) is usually from 1 × 10 ^-10 to 1 × per mol of silver halide.
It is contained in the silver halide emulsion at a ratio of 10 ^-1 mol, preferably 1 x 10 ^{-9 to} 5 x 10 ^-1 mol, more preferably 1 x 10 ^-8 to 2 x 10 ^-2 mol. The ratio (molar ratio) of the sensitizing dye to the compound represented by the general formula (S1) may be any value, but the sensitizing dye / the compound of (S1) = 1000/1 to 1/10
A range of 00 is advantageously used, especially a range of 100/1 to 1/10.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostil compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensates (for example, US Pat. Patent 3,74
3,510), cadmium salts, azaindene compounds and the like. US Patent No. 3,61
5,613, 3,615,641, 3,61
The combinations described in 7,295 and 3,635,721 are particularly useful.

Next, the compound represented by formula (S2) will be described in more detail. In the general formula (S2), R ₆₁ is an aliphatic group (the details thereof are the same as R ₁₁ , but has 1 to 36, preferably 1 to 30), an aryl group (preferably 6 carbon atoms). Aryl groups such as phenyl and naphthyl, and acyl groups (preferably having 2 to 3 carbon atoms).
6 acyl groups such as acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy)
Butyryl, myristoyl, stearoyl, naphthoyl,
m-pentadecylbenzoyl, isonicotinoyl), alkyl or arylsulfonyl group (preferably having 1 carbon atom)
An alkyl or aryl sulfonyl group of, for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), an alkyl or aryl sulfinyl group (preferably an alkyl or aryl sulfinyl group having 1 to 40 carbon atoms, for example, methane sulfinyl, benzene sulfinyl) A carbamoyl group (including an N-substituted carbamoyl group, preferably having 1 to 40 carbon atoms)
Carbamoyl groups such as N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), a sulfamoyl group (including an N-substituted sulfamoyl group, preferably a sulfamoyl group having 0 to 40 carbon atoms such as N-
Methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (preferably An alkoxycarbonyl group having 2 to 36 carbon atoms such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl or an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms); Phenoxycarbonyl, naphthoxycarbonyl). R ₆₂ represents a group as defined for groups represented by hydrogen atom or R _61.

R ₆₁ and R ₆₂ may be bonded to each other to form a 5- to 7-membered ring. For example, a succinimide ring, phthalimide ring, triazole ring, urazole ring, hydantoin ring, 2-oxo-4-oxazolidinone ring No. Each group of the compound represented by formula (S2) may be further substituted with a substituent. Examples of these substituents include an aliphatic group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, and an arylamino. Group,
Examples include a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a hydroxyamino group.

In the general formula (S2), R ₆₂ is a hydrogen atom, an aliphatic group or an aryl group, and R ₆₁ is an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group,
Sulfamoyl, alkoxycarbonyl and aryloxycarbonyl groups are preferred, more preferably R ₆₂ is an aliphatic group, and R ₆₁ is an acyl group,
Compounds that are a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. In R ₆₂ is an alkyl group, and R ₆₁ is an acyl group, and it is most preferable to carbamoyl groups.

The compound represented by the general formula (S2) has a total carbon number of 12 for the purpose of imparting diffusion resistance.
It is preferable that it is above. In the general formula (S2),
General formula (S3), General formula (S4) and General formula (S5)
The compound represented by is preferred.

[0084]

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In the formula, R ₇₁ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. R ₇₂ is a branched alkyl group having 20 or more carbon atoms, a linear or branched alkenyl group having 17 or more carbon atoms, and at least one alkoxycarbonyl group;
Carbon number having as a substituent a group selected from alkenoxycarbonyl, aryloxycarbonyl, carbamoyl, acyl, alkoxy, alkylthio, arylthio, alkyl or arylsulfonyl, aryl and heterocyclic groups Represents 12 or more substituted alkyl groups or substituted alkenyl groups.

[0086]

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In the formula, R ₈₁ represents a hydrogen atom or a group having 1 to 1 carbon atoms.
30 represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group or cycloalkenyl group;
₈₂ represents a substituted or unsubstituted bicycloalkyl group or bicycloalkenyl group having 5 to 30 carbon atoms.

[0088]

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In the formula, R ₉₁ has the same meaning as R ₈₁ , R ₉₂ represents a substituted or unsubstituted alkyl group or an aryl group, and R ₉₃ represents a hydrogen atom or a group represented by R ₉₂ . However, the total number of carbon atoms contained in R ₉₁ , R ₉₂ and R ₉₃ is 12 or more. Hereinafter, the general formula (S3) will be described in detail. In the formula (S3), R ₇₁ represents a substituted or unsubstituted alkyl group. R ₇₁ may be unsubstituted or substituted by a substituent. R ₇₁ has 1 to 6 carbon atoms. Preferred specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t.
-Butyl, n-pentyl, isopentyl, neopentyl, n-hexyl.

Examples of the substituent of these alkyl groups include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group,
Alkylthio group, arylthio group, cyano group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxyl group, acyl group, acyloxy group, alkyl or arylsulfonyl group, acylamino group, alkyl or arylsulfonamide group, and the like,
Specific examples include 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl, 3-methylthiopropyl, 2-acetylaminoethyl, 3-hydroxypropyl, 2-acetyloxyethyl, 3-chloroethyl, 3-methoxyethylallyl, prenyl. R ₇₁ is preferably an unsubstituted alkyl group, and particularly preferably a methyl group.

R ₇₂ represents an alkyl group. The alkyl group may be substituted or unsubstituted. R ₇₂ is preferably
A branched alkyl group having 20 or more carbon atoms, a linear or branched alkenyl group having 17 or more carbon atoms, and at least one alkoxycarbonyl group, alkenoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acyl group,
It represents a substituted alkyl or substituted alkenyl group having a total of 12 or more carbon atoms having, as a substituent, a group selected from an alkoxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an aryl group and a heterocyclic group.

This will be described in more detail below. When R ₇₂ is an alkyl group, the unsubstituted alkyl group is preferably a branched alkyl group having 20 to 60 carbon atoms. Specific examples thereof include the following structures.

[0093]

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When R ₇₂ is a linear or branched alkenyl group having 17 to 60 carbon atoms, specific examples thereof include 1
-Octadecenyl and 2-octadecenyl.

When R ₇₂ is an alkyl or alkenyl group having a total of 12 or more and 60 or less carbon atoms substituted by at least one substituent, the substituent to be substituted on the alkyl group may be an alkoxycarbonyl group or an alkenocarbonyl group. A xycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acyl group, an alkoxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an aryl group, or a heterocyclic group.

Among these, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and an amino group (including an anilino group) are preferred. Specific examples are given below. An alkoxy group (having 1 to 22 carbon atoms such as methoxy, ethoxy, n
-Propoxy, isopropoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy,
Stearyloxy, dodecyloxy, eicosyloxy, docosyloxy, oleyloxy). Examples of the alkoxy group include fine oxocol (trade name, 140, 1600, 1800, 180, 1) manufactured by Nippon Chemical Industry Co., Ltd.
Specific examples include alkoxy groups derived from higher alcohols of 80N, 2000 and 2600.

Aryloxy group (C6-16; for example, phenoxy, p-methoxyphenoxy, m-octyloxyphenoxy, o-chlorophenoxy, 2,4-di-t-octylphenoxy); An alkoxycarbonyl group (having 2 to 23 carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, isopropoxycarbonyl, t-butoxycarbonyl, n-octyloxycarbonyl, n-dodecyloxycarbonyl, pentadecyloxycarbonyl, stearyl Oxycarbonyl, oleyloxycarbonyl, docosyloxycarbonyl). Further, examples of the alkoxycarbonyl group include fine oxocol (trade name, manufactured by Nippon Chemical Industry Co., Ltd.) and 14
0, 1600, 1800, 180, 180N, 200
Specific examples also include alkoxycarbonyl groups derived from 0, 2600 higher alcohols.

Aryloxycarbonyl group (having 6 to 6 carbon atoms)
17. For example, phenoxycarbonyl, p-ethoxyphenoxycarbonyl, m-dodecyloxyphenoxycarbonyl, o-fluorophenoxycarbonyl, 2,4-di-t-octylphenoxycarbonyl). Carbamoyl groups (3-37 carbon atoms; for example, dimethylcarbamoyl, diethylcarbamoyl, dioctylcarbamoyl, distearylcarbamoyl, dioleylcarbamoyl, bis-
(2-ethylhexyl) carbamoyl, stearyloxypropylcarbamoyl), amino group (having 1-2 carbon atoms)
2. For example, octylamino, dioctylamino, stearylamino, distearylamino, oleylamino, dioleylamino, methylamino, anilino)

A preferred structure of the compound represented by formula (S3) is that wherein R ₇₁ is a substituted or unsubstituted alkyl having 1 to 6 carbon atoms, and R ₇₂ is represented by the following formula (S3-1). It is.

[0100]

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In the general formula (S3-1), R ₇₃ has 2 to 2 carbon atoms.
20 is an alkylene group or alkenylene group, R ₇₄ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
0 represents a substituted or unsubstituted heterocyclic group. L ₇₁ is -C
_{O -, - SO 2 -,} - O -, - S -, - COO -, - C
ON ( _R75 )-. R ₇₅ is a hydrogen atom or carbon number 1
-18 represents a substituted or unsubstituted alkyl group. However, when L ₇₁ represents —O—, R ₇₄ has 1 to 40 carbon atoms.
Is a substituted or unsubstituted alkyl group. Where R ₇₃ , L
The total number of carbon atoms of ₇₁ and R ₇₄ is 12 or more.

In the formula (S3-1), R ₇₃ has 2 to 20 carbon atoms.
Represents an alkylene group or alkenylene group, preferably a 1,2-ethylene group, a 1,3-propylene group and a substituted 1,2-ethylene group. Specific examples of R _73.

[0103]

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R ₇₄ is preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 30 carbon atoms.
Among them, a substituted or unsubstituted alkyl group or alkenyl group having 6 to 22 carbon atoms is more preferable. L ₇₁ is -CO-,
_{-O -, - SO 2 -,} - S -, - COO -, - CON
(R ₇₅ ) —. Among them, L ₇₁ is -O-, -CO
—O— and —CO—NR ₇₅ — are preferred.

Among them, R ₇₄ -L ₇₁ -represents an alkoxycarbonyl group, an alkenoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acyl group, an alkoxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, or Preferably it represents an aryl group. The total number of carbon atoms of R ₇₄ , L ₇₁ and R ₇₃ is preferably 12 or more and 60 or less.

Among the compounds represented by formula (S3), the most preferred are compounds represented by the following formula (S3-2).

[0107]

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In the general formula (S3-2), R₇₁Has 1 to 1 carbon atoms
6 represents a substituted or unsubstituted alkyl group;₇₅,
R₇₆, R₇₇, R₇₈Are independently the same or different
Well, hydrogen atom, substituted or unsubstituted with 1 to 18 carbon atoms
Alkyl group or substituted or absent of 2 to 18 carbon atoms
X represents -OR₇₉Or -N (R
₇₉) (R₈₀) And R₇₉And R₈₀Are independently
A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms;
A substituted or unsubstituted alkyl group having 2 to 22 carbon atoms
Or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms.
Indicates a reel group. R₇₁Is a methyl group, an ethyl group or n
-Hexyl groups are preferred. R₇₅, R₇₆, R ₇₇, R₇₈Lotus
All hydrogen atoms or R₇₅, R₇₆, R₇₇, R₇₈Less of
One of which is an alkyl or alkenyl group having 5 to 18 carbon atoms
Are preferable, and the other is preferably a hydrogen atom.
New R₇₉Is an alkyl group or alkenyl having 6 to 22 carbon atoms
Preferred is a thiol group. Where R₇₅, R₇₆, R₇₇, R₇₈Tear
When all are hydrogen atoms, R₇₉Preferably has 14 or more carbon atoms
New R₈₀Is preferably an alkyl group having 6 to 18 carbon atoms.
X is -OR₇₉Is -NR₇₉R₈₀More preferred.

The most preferred 1 in the general formula (S3-2)
In one structure, R ₇₅ is an alkenyl group or an alkyl group having 12 to 18 carbon atoms, R ₇₆ , R ₇₇ , and R ₇₈ are hydrogen atoms, and R ₇₁ is a methyl group, an ethyl group, or an n-hexyl group. , X is —OR ₇₉ and R ₇₉ is an alkyl or alkenyl group having 12 to 18 carbon atoms.

The other one of the general formula (S3-2)
A preferred structure is R₇₇Is alkenyl having 12 to 18 carbon atoms
Group or an alkyl group;₇₅, R₇₆, R₇₈Is a hydrogen atom
And R₇₁Is a methyl group, an ethyl group or n-hexyl
X is -OR₇₉And R₇₉Has 12 to 1 carbon atoms
8 alkyl or alkenyl group. General formula
Another most preferred structure in (S3-2) is R
₇₅, R₇₆, R₇₇, R₇₈Are all hydrogen atoms, and R₇₁But
X is a methyl group, an ethyl group or an n-hexyl group;
OR₇₉And R₇₉Is an alkyl group having 12 to 18 carbon atoms or
Is of an alkenyl group. Used in the present invention described above
Of the most preferred compounds are R₇₅, R₇₆,
R ₇₇, R₇₈Are all hydrogen atoms, and R₇₉Is myristil
Group, palmityl group or stearyl group,₇₁But
It is the case of a tyl group, an ethyl group or an n-hexyl group.

The compound represented by formula (S2) preferably has a molecular weight of 250 or more, more preferably 300 or more, and most preferably 330 or more. Next, the general formula (S4) will be described in detail. R in the general formula (S4)
₈₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group. When R ₈₁ represents an alkyl group or an alkenyl group, R ₈₁ preferably has 1 to 6 carbon atoms.
It is. Preferred specific examples thereof include methyl, ethyl, allyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and prenyl. As the substituents of these alkyl groups and alkenyl groups, for example, alkyl groups, alkenyl groups, aryl groups,
Heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, cyano group,
A nitro group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, an acyl group, an acyloxy group, an alkyl or arylsulfonyl group, an acylamino group, an alkyl or arylsulfonamide group, and the like, and specific examples include 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl, 3-methylthiopropyl, 2-acetylaminoethyl, 3-hydroxypropyl, 2-acetyloxyethyl, 3-chloroethyl, 3-methoxyethylallyl, prenyl . When R ₈₁ represents a cycloalkyl group or a cycloalkenyl group, R ₈₁ preferably has 5 to 12 carbon atoms. To give a preferred specific example,
Examples include a cyclopentyl group, a cyclohexyl group, a 1-cyclohexen-1-yl group, and a 2-cyclohexen-1-yl group. R ₈₁ is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group.

R ₈₂ represents a substituted or unsubstituted bicycloalkyl or bicycloalkenyl group having 5 to 30 carbon atoms. R ₈₂ is preferably [2, 2, 1], [2,
Those having a 2,2], [1,1,1] or [2,1,1] bicyclo ring structure are preferred.

The term “bicycloalkyl group” as used herein refers to a monovalent aliphatic hydrocarbon formed by removing one hydrogen of a bicycloalkane, that is, an aliphatic saturated hydrocarbon consisting only of two rings sharing two or more atoms. And a bicycloalkenyl group is defined as a bicycloalkenyl group having at least one double bond.
An aliphatically unsaturated hydrocarbon consisting of only two rings sharing at least one atom, that is, a monovalent group formed by removing one hydrogen of a bicycloalkene.

Among the compounds represented by formula (S4), preferred are compounds represented by formulas (S4-1) and (S4-
It is represented by 2).

[0115]

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In the formulas (S4-1) and (S4-2), R
₈₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an alkenyl group or a cycloalkenyl group, and R ₈₃ and R ₈₄ may be independently the same or different Often a hydrogen atom or 1 to 3 carbon atoms
Represents a substituted or unsubstituted alkyl group of 0. Q ¹ ,
Q ² and Q ³ each independently represent an atomic group necessary for bonding to carbon atoms at both ends to form a bicyclo ring.

Examples of R ₈₁ include the specific examples described for R ₈₁ in the formula (S4). The same applies to preferred examples.
R ₈₃ and R ₈₄ preferably have 1 to 20 carbon atoms, and have 1 to 8 carbon atoms.
Is more preferred. Specific examples of R ₈₃ and R ₈₄ are represented by the formula (S
_Examples of R81 described in 4) can be given. R ₈₃ and R ₈₄ are preferably a hydrogen atom or a methyl group.

Q ¹ , Q ² and Q ³ are preferably [1,
[1,1], [2,1,1], [2,2,1], [2,
Those which form a 2,2] bicyclo ring are preferred. Among them, those forming a [2,2,1] or [2,2,2] ring are preferable. In the formula (S4-1), those forming a [2,2,1] ring are preferable. In the equation (S4-2),
Those which form a [2,2,2] ring are preferred.

The preferred structure of the compound represented by formula (S4-1) is that R ₈₁ is an alkyl group having 1 to 6 carbon atoms, R ₈₃ and R ₈₄ are hydrogen atoms, and Q ¹ , Q ² , and forms a [2,2,1] bicyclo ring Q ^3. A preferred structure of the compound represented by the general formula (S4-2) is
R ₈₁ is an alkyl group having 1 to 6 carbon atoms, R ₈₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q ¹ ,
Q ² and Q ³ form a [2,2,2] bicyclo ring.

A more preferred structure of the compound represented by formula (S4) is a structure represented by formula (S4-6).

[0121]

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[0122] In the general formula (S4-6), R ₈₁ has the same meaning as R ₈₁ in the general formula (S4). X 'is -OR _{8k or-}
NR _8K R _8l , wherein R _8k and R _8l may be the same or different and are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 6 to 30 carbon atoms. Represents a substituted aryl group or a substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms. R _8k and R ₈₁ may combine with each other to form a ring structure. R _8a , R _8b , R _8c , R _8d ,
R _8e , R _8f , R _8g , R _8h , R _8i and R _8j may be each independently the same or different, and represent a hydrogen atom or a carbon atom
6 is a substituted or unsubstituted alkyl group. Also, R _8c and R
_8f may combine to form a double bond.

Specific examples and preferred examples of [0123] R ₈₁ is the same as R ₈₁ in formula (S4). X ′ is preferably —OR _8k , and R _8k is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms. R
_{When 8k} is an alkyl group, it may be branched or linear. At this time, the substituent to be substituted on the alkyl group includes an alkyl group, a halogen atom, a carboxyl group, an aryl group, a cyano group, a sulfamoyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, and an aryloxy group. Carbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, heterocyclic group, alkyl A sulfonyl group and an arylsulfonyl group. Specific examples of the alkyl group represented by R _8k are as follows.

[0124]

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In addition, the alkyl groups described for R ₈₁ can also be mentioned as specific examples. -OR _8k further includes fine oxocol (trade name, manufactured by Nissan Chemical Industries, Ltd.)
140, 1600, 1800, 180, 180N, 20
Specific examples also include alkoxy groups derived from higher alcohols of 00 and 2600. Specific examples of the alkenyl group include allyl, homoallyl, prenyl, and geranyl. Specific examples of the aryl group include phenyl, 2
-Naphthyl and 2,4-di-t-pentylphenyl. R _8a , R _8b , R _8c , R _8d , R _8e , R _8f , R _8g ,
Specific examples of R _8h , R _8i and R _8j include a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl and n-pentyl. R _8a and R _8b are preferably a hydrogen atom at the same time or a methyl group at the same time. It is preferable that R _8c and R _8f simultaneously form a hydrogen atom or form a double bond by bonding.
R _8d , R _8e , R _8g , R _8h , R _8i and R _8j are preferably a hydrogen atom.

More preferred structures represented by formula (S4-6) are those represented by formula (S4-4) or (S4-5)
It is represented by

[0127]

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In the formulas (S4-4) and (S4-5), R
₈₁ has the same meaning as R _{81 in} formula (S4). R ₈₁ preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₈₁ is more preferably an alkyl group having 1 to 6 carbon atoms, and among them, R ₈₁ is methyl, ethyl, n-
Propyl and n-hexyl are more preferred. X "is -OR
₈₅ or —N (R ₈₅ ) (R ₈₆ ), wherein R ₈₅ and R ₈₆ are each independently a hydrogen atom which may be the same or different, or
Represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. R ₈₅ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. R ₈₅ is particularly preferably an alkyl group having 10 to 22 carbon atoms. Among them, X ″ is preferably —O—R ₈₅ , and R ₈₅ is a carbon number of 14, 16, 1 or
8, 20, 22 linear alkyl groups, or -N
(R ₈₅ ) In (R ₈₆ ), R ₈₅ and R ₈₆ are a hydrogen atom or a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, and R ₈₁ is an unsubstituted alkyl group having 1 to 6 carbon atoms. . Among them, X ″ is more preferably —N (R ₈₅ ) (R ₈₆ ) and R ₈₅ , R _85
86 is a substituted or unsubstituted alkyl group having 8 to 18 carbon atoms, and R ₈₁ is a methyl group, an ethyl group, an n-propyl group or an isopropyl group.

Some of the compounds of the present invention have an enantiomer, and in this case, either an optically active compound or a racemic compound can be used for the purpose. Preferably, the racemic form is preferred in that the cost is low.

Next, the general formula (S5) will be described in detail.
I do. R₉₁Is R, including its preferred₈₁Synonymous with
is there. R₉₂Is a substituted or unsubstituted alkyl group or
An aryl group;₉₃Is a hydrogen atom or R₉₂At
It has the same meaning as the group shown. R₉₂Is an alkyl group
If the details are R _8kSame as the description of the alkyl group
The same. R₉₂Is an aryl group, the aryl group
R_8kIs a substituent that is substituted when is an alkyl group.
The substituents exemplified above may be substituted, for example, 4-
Palmitoylaminophenyl, 3-pentadecylphenyl
And 3-hexadecyloxyphenyl. Where R
₉₁, R₉₂And R₉₃The total number of carbons contained in is 12 or more
It is.

Among the compounds represented by the general formula (S2), the compounds represented by the general formulas (S4) and (S5) are particularly preferable, and the compound represented by the general formula (S4) is more preferable. Next, specific examples of the compound represented by the general formula (S2) are shown, but it should not be construed that the invention is limited thereto.

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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The compound represented by formula (S2) is described in J.
Org. Chem., 27, 4054 ('62), J. Amer. Chem. Soc., 7
3, 2981 ('51), JP-B-49-10692, or the like, or a method analogous thereto. The compound represented by formula (S2) can be used in any layer in the light-sensitive material. That is, a light-sensitive layer (a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer), a non-light-sensitive layer (for example, a protective layer, a non-light-sensitive fine-grain silver halide emulsion layer, It can be used for any of the intermediate layer, filter layer, undercoat layer and antihalation layer, but is preferably used for the emulsion layer. Next, the compound (S
2-67) shows the synthesis method. The synthetic route is shown in Scheme 2.

[0156]

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Synthesis of (S2-67b) Di-n-octylamine 50.3 g, acetonitrile 1
Then, under ice-cooling, 34.2 g of (S2-67a) was mixed with 50 ml of acetonitrile.
The solution dissolved in ml was dropped. At this time, the reaction solution was dropped so that the temperature became 15 to 18 ° C. After reacting for 15 minutes, water and ethyl acetate were added to carry out a liquid separation. The organic layer was washed twice with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain (S2-67b). (S2-67b) was obtained. (S2-67b) was used in the next step as it was. Synthesis of (S2-67c) (S2-67b) 50 ml of methylene chloride and 0.3 ml of dimethylformamide were added to and dissolved in the whole amount, and thionyl chloride 2
9.7 g was dropped at 20 ° C. After reacting at 40 ° C for 20 minutes, the remaining thionyl chloride and methylene chloride were distilled off under reduced pressure by an aspirator to obtain (S2-67c). (S2-67c) was used in the next step as it was. Synthesis of (S2-67) 250 ml of water, 10.4 g of sodium hydroxide, and 21.7 g of N-methylhydroxylamine hydrochloride were dissolved at 10 ° C. in a stream of nitrogen gas. Then sodium bicarbonate 43.7
g and 300 ml of ethyl acetate were added thereto, and a solution obtained by dissolving the total amount of (S2-67c) in 100 ml of ethyl acetate was added at a reaction temperature of 15 to 100 ml.
It was lowered while maintaining at 20 ° C. The reaction solution was heated to 50 ° C. to perform liquid separation. The organic layer was washed twice with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was crystallized from acetonitrile. The obtained crude crystals are washed with hexane 2
After dissolving in 5.0 ml of water and filtering while hot, the filtrate was distilled off under reduced pressure and then recrystallized with a mixed solvent of 50 ml of ethyl acetate, 25 ml of methanol and 250 ml of acetonitrile to give (S
2-67) was obtained. (Yield 33.4%). 300 MHz ¹ HNMR spectrum _{δ (CDC1 3): 0.90 (} 3H, t), 0.91
(3H, t), 1.06-1.41 (20H, m),
1.41 to 1.92 (6H, m), 2.82 to 3.77
(8H, m), 3.16 (3H, s), 5.85-6.
20 (1H, m), 6.40 to 6.68 (1H, m) In the present invention, the compound represented by the general formula (S2) is a water-soluble solvent such as water, methanol, or ethanol, or a mixed solvent thereof. And may be added by emulsification and dispersion. Further, they may be added in advance during the preparation of the emulsion. In the case of dissolving in water, if the solubility is increased by increasing or decreasing the pH, the pH may be increased or decreased and dissolved, and then added. In the present invention, two or more of the compounds represented by formula (S2) may be used in combination. For example, a combination of a water-soluble substance and an oil-soluble substance is advantageous in photographic performance. The coating amount of the compound represented by the general formula (S2) in the silver halide photographic light-sensitive material is 10 ⁻⁴ mmol / m ^{2 to} 10 mmol /.
m ² is preferable, and 10 ⁻³ mmol / m ^{2 to} 1 mmol / m ² is more preferable.

The process for producing a silver halide emulsion is roughly divided into processes such as grain formation, desalting and chemical sensitization. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The present invention can be preferably used for reduction-sensitized emulsions. Applying reduction sensitization to a silver halide emulsion may be performed in basically any step. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. Here, growing is also referred to as a method of performing reduction sensitization in a state where silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. The method also includes a method of further growing after subjecting to reduction sensitization in a heated state.

The reduction sensitization of the present invention refers to a method in which a known reducing agent is added to a silver halide emulsion, or a pA called silver ripening.
a method of growing or ripening in an atmosphere of low pAg of g1-7, a high p of pH8-11 called high pH ripening
Either a method of growing in an atmosphere of H or a method of ripening can be selected. Also, two or more methods can be used in combination.

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

As the reduction sensitizer, there are known, for example, a first silver salt, an amine and a polyamic acid, a hydrazine derivative, formamidinesulfinic acid, a silane compound and a borane compound. In the present invention, these known compounds can be selected for use, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-7 to 10 ^-3 mol per mol of silver halide.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention. Ascorbic acid and its derivatives (hereinafter, “ascorbic acid compound”
That. The following can be mentioned as specific examples of ()). (A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-o-isopropylidene

Ascorbic acid compound used in the present invention
Is the addition amount at which the reduction sensitizer is conventionally preferably used.
It is desirable to use a large amount in comparison. For example,
No. 33572 states that the amount of reducing agent is usually
0.75 × 10^-2Milliequivalent (8 × 10^-FourMol / AgX mol)
I can't. 0.1 to 10 mg per kg of silver nitrate (Asco
As rubic acid, 10^-7~Ten^-FiveMol / AgX mol)
If effective. (The converted value is based on the inventors.)
Has been described. US 2,487,850 states that "Reduction sensitization
The amount of tin compound that can be used as an agent is 1
× 10^-7~ 44 × 10 ^-6Mol ". See also
No. 7-179835 describes the addition amount of thiourea dioxide
About 0.01 mg to about 2 mg per mole of silver halide, stannous chloride
It is stated that about 0.01 mg to about 3 mg is appropriate to use.
doing. The ascorbic acid compound used in the present invention is
Emulsion grain size, halogen composition, emulsion preparation temperature, p
The preferable addition amount depends on factors such as H and pAg.
5 × 10 5 per mole of silver halide^-Five~ 1 × 10^-1Mole
It is desirable to select from the range. More preferably 5 ×
Ten^-FourMol ~ 1 x 10^-2Prefer to choose from a range of moles
No. Particularly preferred is 1 × 10^-3Mol ~ 1 x 10^-2Molar range
Choose from the box.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides, and can be added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Further, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, and silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (eg, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaC
_{O 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2Na 2 SO 4
.H ₂ O ₂ .2H ₂ O), peroxyacid salt (for example, K ₂ S ₂₎
O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds {eg, K ₂ (Ti (O ₂ ) C ₂ O ₄ ) .3H ₂ O, 4K ₂ S
O ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ [VO
Oxygenates such as (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O｝, permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), iodine and bromine And the like, salts of perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferric acid), and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T, chloramine B). ) Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfinates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The oxidizing agent particularly preferred in the present invention is selected from the compounds represented by the following formulas (XX), (XXI) or (XXII).

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In the formula, R ₁₀₁ , R ₁₀₂ and R ₁₀₃ represent an aliphatic group, an aryl group or a heterocyclic group, M ₁₀₁ represents a cation, E represents a divalent linking group, a represents 0 or 1
It is.

The general formulas (XX), (XXI) and (XXII) will be described in more detail. When R ₁₀₁ , R ₁₀₂ and R ₁₀₃ are an aliphatic group, they are preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which has a substituent. May be. Examples of the alkyl group include methyl, ethyl, propyl, butyl,
Pentyl, hexyl, octyl, 2-ethylhexyl,
Decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, t-butyl.
Examples of the alkenyl group include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.

The aryl group represented by R ₁₀₁ , R ₁₀₂ and R ₁₀₃ preferably has 6 to 20 carbon atoms and includes, for example, a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group represented by R ₁₀₁ , R ₁₀₂ and R ₁₀₃ is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium,
For example, pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tetrazole ring, triazole ring , Benzotriazole ring, tetrazole ring,
An oxadiazole ring and a thiadiazole ring are exemplified.

Examples of the substituent of R ₁₀₁ , R ₁₀₂ and R ₁₀₃ include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), and an aryl group (phenyl, naphthyl, tolyl) ), A hydroxy group, a halogen atom (for example, fluorine,
Chlorine, bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl, valeryl), sulfonyl group (eg, methylsulfonyl, Phenylsulfonyl), acylamino groups (eg, acetylamino, benzamino), sulfonylamino acids (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy groups (eg, acetoxy, benzoxy), carboxyl groups, cyano groups, sulfo groups, amino groups and the like. Can be

E is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of E include-(CH ₂ ) _n- (n = 1 to 12) and -CH ₂ -CH = C
H-CH ₂ -,

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A xylylene group and the like can be mentioned. Examples of the divalent aromatic group of E include phenylene and naphthylene.

M ₁₀₁ is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (tetraphenylphosphonium), and a guanidine group.

Specific examples of the compound represented by formula (XX), (XXI) or (XXII) are shown below, but the present invention is not limited thereto.

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The compound of the formula (XX) is disclosed in JP-A-54-1.
No. 019 and British Patent 972,211.

The compound represented by formula (XX), (XXI) or (XXII) is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. 10 ^-6 to 10 ^-2 , especially
An addition amount of 10 ^-5 to 10 ^-3 mol / mol Ag is preferable.

The compound represented by the general formula (XX), (XXI) or (XXII) can be added during the production process according to a method usually used for adding an additive to a photographic emulsion. For example, a water-soluble compound is an aqueous solution of an appropriate concentration, and a compound insoluble or hardly soluble in water is a suitable organic solvent miscible with water, for example, alcohols, glycols, and the like.
Among ketones, esters, amides and the like, they can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution.

The compound represented by the general formula (XX), (XXI) or (XXII) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization.
Preferred is a method in which a compound is added after or during reduction sensitization. Particularly preferred is a method of adding during the grain growth.

It is possible to add to the reaction vessel in advance, but it is preferable to add at an appropriate time during the particle formation. Alternatively, the compound of the general formula (XX), (XXI) or (XXII) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. The general formulas (XX) and (XXI)
Alternatively, it is also a preferable method to add the solution of the compound (XXII) several times or to add it continuously for a long time.

Among the compounds represented by formula (XX), (XXI) or (XXII), the most preferred compound for the present invention is a compound represented by formula (XX).

The silver halide emulsion of the present invention is preferably sensitized with gold / chalcogen. Chalcogen sensitization is performed with at least one of a selenium sensitizer, a sulfur sensitizer, and a tellurium sensitizer.

Here, selenium sensitization is carried out by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
Preferably, the emulsion is stirred at a temperature of 40 ° C. or higher for a certain time. Selenium sensitization using an unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides,
Selenocarboxylic acids and esters, selenophosphates are mentioned. Particularly preferred unstable selenium compounds are those shown below.

I. Colloidal metal selenium II. Organic selenium compound (a selenium atom is double-bonded to a carbon atom of an organic compound by a covalent bond) a. Isoselenocyanates, for example, aliphatic isoselenocyanates such as allyl isoselenocyanate b. Selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetraoctyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N Aliphatic selenoureas such as dimethyl, diethyl, dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl; heterocyclic having heterocyclic groups such as pyridyl, benzothiazolyl Selenourea c. Selenoketones For example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to> C = Se, selenobenzophenone d. Selenoamides, for example, selenoacetamide e. Selenocarboxylic acids and esters, for example, 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate III. Others a. Selenides, for example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates, for example, tri-p-tolylselenophosphate, tri-
n-butylselenophosphate

Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will recognize that the labile selenium compound as a sensitizer for photographic emulsions is not critical in the structure of the compound as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule is It is generally understood that selenium has no role except to carry it in an unstable form in the emulsion. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

JP-B-46-4553, JP-B-52-3
Selenium sensitization using a non-unstable selenium sensitizer described in JP-B-4491 and JP-B-52-34492 can also be used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione,
-Selenoxodinthiones and their derivatives.

The non-labile selenium sensitizers described in JP-B-52-38408 and thioselenazolidinedione compounds are also useful.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent and added during chemical sensitization. Preferably, the selenium sensitizer is added before the start of chemical sensitization. Is done. The selenium sensitizer used is not limited to one type, and two or more of the above-mentioned selenium sensitizers can be used in combination. In particular, a combination of an unstable selenium compound and a non-unstable selenium compound is preferable.

The addition amount of the selenium sensitizer used in the present invention varies depending on, for example, the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, but preferably 1 × 1 per mole of silver halide
It is 0 ^-8 mol or more, more preferably 1 × 10 ^-7 mol or more and 1 × 10 ^-4 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C or higher, more preferably 50 ° C or higher and 80 ° C or lower. pAg and pH
Is optional. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

In the present invention, selenium sensitization is more effectively performed in the presence of a silver halide solvent.

Examples of the silver halide solvent usable in the present invention include, for example, US Pat. No. 3,271,
No. 157, No. 3,531,289, No. 3,57
4,628, JP-A-54-1019, JP-A-54-15
(A) Organic thioethers described in JP-A-8917, JP-A-53-82408, JP-A-55-77737, and JP-A-5-77737;
(B) a thiourea derivative described in JP-A-5-2982, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. (D) imidazoles, (e) sulfites described in JP-A-54-100717,
(F) thiocyanate.

Particularly preferred solvents include thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the preferable amount is 1 to 1 mol per mol of silver halide.
It is not less than × 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

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

In the sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine can be mentioned. In addition, for example, U.S. Patent Nos. 1,547,944 and 2,410,689,
No. 2,278,947 and No. 2,728,668
No. 3,501,313, No. 3,656,95
Sulfur sensitizers described in the specifications of JP-A-5, German Patent 1,422,868, JP-B-56-24937, and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can vary over a considerable range under various conditions such as pH, temperature, silver halide grain size, but may vary from 1 × 10 5 per mole of silver halide.
^It is preferably from ^-7 mol to 1 × 10 ^-4 mol.

As the gold sensitizer for gold sensitization in the present invention, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold.

The amount of the gold sensitizer to be added varies depending on various conditions. As a guide, the amount is 1 × 10 ^-7 per mol of silver halide.
It is preferably from 1 mol to 1 × 10 ^-4 mol.

The gold / chalcogen sensitization is gold / sulfur sensitization,
Selenium sensitization, gold / tellurium sensitization / gold / sulfur / selenium sensitization
Any of gold, sulfur, tellurium sensitization, gold, selenium, tellurium sensitization and gold, sulfur, selenium, tellurium sensitization can be used.

The emulsion of the present invention is preferably tabular silver halide grains having an aspect ratio of 3 or more, more preferably 5 or more. Here, the tabular grains mean 1
It is a general term for particles having two twin planes or two or more parallel twin planes. In this case, the twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship. These tabular grains have a triangular, hexagonal or rounded circular shape when the grains are viewed from above, and the triangular ones are triangular, the hexagonal ones are hexagonal, circular. Have circular outer surfaces parallel to each other.

In the present invention, the aspect ratio of the tabular grains refers to a value obtained by dividing each grain diameter by the thickness of the tabular grains having a grain diameter of 0.1 μm or more. The measurement of the particle thickness is performed by evaporating a metal from the diagonal direction of the particles together with the reference latex, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. Easy.

In the present invention, the particle diameter is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The diameter of the tabular grains is 0.15 to 5.0 μm
It is preferred that The thickness of tabular grains is 0.05
It is preferably about 1.0 μm.

The average aspect ratio is determined as an arithmetic average of the aspect ratios of at least 100 silver halide grains. It can also be determined as the ratio of the average diameter to the average thickness of the particles.

The emulsion of the present invention preferably contains tabular silver halide grains having an aspect ratio of 3 or more, preferably tabular silver halide grains having an aspect ratio of 5 or more, and preferably 60% of the total projected area. The above is occupied by such tabular silver halide grains. The proportion occupied by tabular grains is preferably at least 60%, particularly preferably at least 80%, of the total projected area.

When monodispersed tabular grains are used, more preferable results may be obtained. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-1516.
According to the description of No. 18, etc., the shape is briefly described as follows: 70% or more of the total projected area of the silver halide grains is the length of the side having the maximum length to the length of the side having the minimum length. Is occupied by tabular silver halide having a hexagonal shape having a height ratio of 2 or less and having two parallel surfaces as outer surfaces, and further, a grain size distribution of the hexagonal tabular silver halide grains. Coefficient of variation (variation in grain size (standard deviation) expressed by the circle-converted diameter of the projected area)
Divided by the average particle size) is 20% or less.

Further, the emulsion of the present invention preferably has dislocation lines. Dislocations in tabular grains are, for example, JF Hamilto
n, Phot. Sci. Eng., 11, 57 (1967) and T. Shiozawa, J. So
c. Phot. Sci. Japan, 35, 213 (1972) can be observed by a direct method using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for electron microscope observation, and the sample is placed in a manner to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particle, the more difficult it is for an electron beam to pass. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the photographs of the particles obtained by such a method, the position and number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be determined.

The average number of dislocation lines is 10 or more per grain. More preferably, the average is 20 or more per particle.
When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, approximately 10, 20,
It is possible to count as many as thirty, clearly distinguishing it from having only a few. The average number of dislocation lines per particle is determined as the number average by counting the number of dislocation lines for 100 or more particles.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the dislocation starting positions is similar to the particle shape, but may not be a perfect similar shape but may be distorted. This type of dislocation is not found in the central region of the grain. The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of hexagonal tabular silver halide grains as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. . Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the center of two parallel main planes of the tabular grains.
When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane. In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation may be limited to the outer periphery, the main plane, or a local position.
These may be combined and formed. That is, they may be present simultaneously on the outer periphery and on the main plane.

The introduction of dislocation lines on the outer periphery of tabular grains can be achieved by providing a specific high silver iodide layer inside the grains. Here, the case where the high silver iodide layer is provided discontinuously in the high silver iodide layer is included. Specifically, it is obtained by preparing a base grain, providing a high silver iodide layer, and covering the outside with a layer having a lower silver iodide content than the high silver iodide layer. The silver iodide content of the tabular grains of the base is lower than that of the high silver iodide layer, preferably 0 to 20 mol%, more preferably 0 to 15 mol%.

The high silver iodide layer inside the grain is a silver halide solid solution containing silver iodide. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but is preferably silver iodide or silver iodobromide (silver iodide content: 10 to 40 mol%). More preferred. In order for the high silver iodide layer inside the grains (hereinafter referred to as the internal silver high iodide layer) to be selectively present anywhere on the sides or corners of the base grains, the conditions for forming the base grains and the internal It can be controlled by the conditions for forming the high silver iodide layer. As the conditions for forming the base silver grains, pAg (the logarithm of the reciprocal of silver ion concentration) and the presence, type, amount, and temperature of the silver halide solvent are important factors. By performing the pAg at the time of growing the base grains at 8.5 or less, more preferably at 8 or less, the internal high silver iodide layer can be selectively present near the apexes of the base grains. On the other hand, when the pAg at the time of growing the base grains is 8.5 or more, preferably 9 or more, the internal silver iodide-rich layer can be present on the sides of the base grains. These pAg thresholds change up and down depending on the temperature and the presence, type and amount of silver halide solvent. When, for example, thiocyanate is used as the silver halide solvent, the threshold value of this pAg shifts toward a higher value. Particularly important as the pAg during growth is the pAg at the end of growth of the base particle. On the other hand, even when the pAg during the growth does not satisfy the above value, it is possible to control the selected position of the internal silver iodide-rich layer by adjusting the pAg after the growth of the base grains and ripening. is there. At this time, ammonia, amine compounds, and thiocyanate salts are effective as silver halide solvents. The so-called conversion method can be used to form the internal silver iodide-rich layer. In this method, during the grain formation, there is a method of adding a halogen ion having a lower solubility of a salt for forming a silver ion than a halogen ion forming a grain or a vicinity of the surface of the grain at that time. In the present invention, it is preferable that the amount of halogen ions having low solubility added to the surface area of the particles at that time is not less than a certain value (related to the halogen composition).
For example, it is preferable to add a certain amount or more of KI to the surface area of the AgBr particles at that time during the particle formation. Specifically, it is preferable to add 8.2 × 10 ⁻⁵ mol / m ² or more of iodide salt.

A more preferred method for forming an internal silver-rich iodide layer is to add an aqueous silver salt solution simultaneously with the addition of an aqueous halide salt solution containing an iodide salt.

For example, AgNO is added simultaneously with the addition of the KI aqueous solution.
₃ Add the aqueous solution by double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may be shifted before and after each other. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that the pAg at the time of addition of the halide solution containing iodide ions and the addition of the silver salt aqueous solution by double jet decrease with the addition time of the double jet. PAg before starting addition
Is preferably 6.5 or more and 13 or less. More preferably, it is 7.0 or more and 11 or less. PAg at the end of addition is 6.5 or more 10.0
The following are most preferred.

In carrying out the above method, it is preferable that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system when forming a high silver iodide layer is 30 ° C. or more and 70 ° C.
C. or lower is preferred, and more preferably 30 to 50.degree.

Most preferably, the formation of the internal silver iodide-rich layer is fine-grain silver iodide (fine silver iodide; hereinafter the same).
Alternatively, fine grain silver iodobromide, fine grain silver chloroiodide, or fine grain silver chloroiodobromide can be added. In particular, it is preferable to add fine grain silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm,
Fine particles having a particle size of not more than μm or not less than 0.1 μm can also be used. With respect to the method for preparing these fine silver halide grains, JP-A-1-183417 and JP-A-2-4
No. 4335, No. 1-183644, No. 1-183364
No. 5, 2-43534 and 2-43535 can be referred to. An internal high silver iodide layer can be provided by adding and ripening these fine grain silver halides. When the fine particles are dissolved by ripening, the above-mentioned silver halide solvent can be used. It is not necessary that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles dissolve and disappear when the final particles are completed.

The outer layer covering the inner silver iodide-rich layer is lower than the silver iodide content of the high silver iodide layer, and preferably has a silver iodide content of 0 to 30 mol%, more preferably 0 to 30 mol%. 20 mol%,
Most preferably, it is 0 to 10 mol%. The position of this internal silver iodide-rich layer is measured from the center of the hexagon or the like on which the grains are projected.
It is preferably present in the range of 5 mol% to less than 100 mol%, more preferably in the range of 20 mol% to less than 95 mol%, particularly preferably in the range of 50 mol% to less than 90 mol%, based on the total silver content of the grains. Is preferred. The amount of silver halide forming these internal silver iodide-rich layers is not more than 50 mol%, more preferably not more than 20 mol% of the total silver content of the grains. The values of these high silver iodide layers are prescribed values for the production of silver halide emulsions, not the values obtained by measuring the halogen composition of the final grains by various analytical methods. The internal silver iodide-rich layer often disappears in the final grain due to a recrystallization process or the like, and the above all relates to a production method thereof.

Therefore, although dislocation lines can be easily observed in the final grain by the above-described method, the internal silver iodide layer introduced for introducing dislocation lines cannot often be confirmed as a clear layer. For example, in some cases, the entire peripheral region of tabular grains is observed as a high silver iodide layer. X-ray diffraction, EP
MA (also known as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), ESCA (also known as XPS) method (irradiating X-rays and exiting from the grain surface) The method can be confirmed by a combination of a method of dispersing incoming photoelectrons).

The temperature and pAg at the time of forming the outer layer covering the inner silver iodide-rich layer are arbitrary, but the preferred temperature is 30 ° C.
Above, it is below 80 ℃. Most preferably, it is 35 ° C or more and 70 ° C or less. Preferred pAg is 6.5 or more and 11.5 or less. In some cases, it is preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

In order to introduce dislocation lines into the main surface of tabular grains, after preparing base grains, silver halochloride is deposited on the main surface, and the halochloride is converted to high silver bromide or high silver iodide after conversion. A layer may be formed, and a shell may be further provided outside the layer. Examples of the silver halochloride include silver chloride or silver chlorobromide or silver chloroiodobromide having a silver chloride content of 10 mol% or more, preferably 60 mol% or more. The deposition of these silver halochloride base particles on the main plane can be carried out by separately or simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of a suitable alkali metal salt (eg, potassium chloride), or an emulsion comprising these silver salts. Can be deposited by aging with the addition of The deposition of these silver halochlorides is possible in any pAg range, but is most preferably between 5.0 and 9.5. In this method, tabular grains are grown mainly in the thickness direction. The amount of this silver halochloride layer is 1 mol% or more and 80 mol% or less in terms of silver mol% based on the base grains. More preferably, it is 2 mol% or more and 60 mol% or less. By converting this silver halochloride layer with an aqueous halide solution capable of forming a silver salt having lower solubility than silver halochloride, dislocation lines can be introduced on the main plane of the tabular grains. For example, after converting this halo silver chloride layer with KI aqueous solution,
It is possible to grow the shell to obtain the final particles.
The halogen conversion of these silver halochloride layers does not mean that all of them are replaced by silver salts having lower solubility than silver halochloride, but preferably 5% or more, more preferably 10% or more,
Most preferably, it is replaced by a silver salt having a low solubility of 20% or more. By controlling the halogen structure of the base grains on which the silver halochloride layer is provided, it is possible to introduce dislocation lines at local sites on the main plane. For example, when a base grain having an internal silver iodide-rich structure displaced in the lateral direction of the base tabular grain is used, dislocation lines can be introduced only into the main plane of the peripheral part excluding the center part of the main plane. When the base grains having an outer silver iodide-rich structure are displaced in the lateral direction of the base tabular grains, dislocation lines can be introduced only into the central portion excluding the peripheral portion of the main plane. Furthermore, it is also possible to deposit silver halochloride only in a region having a limited area by using a local controlling substance such as iodide for the epitaxial growth of silver halochloride, and to introduce dislocation lines only in that region. The temperature during the deposition of silver halochloride is preferably from 30 ° C. to 70 ° C., more preferably from 30 ° C. to 50 ° C. It is possible to perform conversion after the deposition of the silver halochloride and then grow the shell, but it is also possible to perform the halogen conversion while growing the shell after the deposition of the silver halochloride.

The position of the internal silver halochloride layer formed substantially parallel to the main plane may be present in a range of 5 mol% or more and less than 100 mol% with respect to the silver content of the whole grain on both sides from the center of the grain thickness. Preferably, it is more preferably in the range of 20 mol% or more and less than 95 mol%, particularly preferably in the range of 50 mol% or more and less than 90 mol%.

The silver iodide content of the shell is preferably from 0 to 30.
Mol%, more preferably 0 to 20 mol%. Temperature at the time of shell formation, pAg is optional, but preferred temperature is 30 ° C
Not less than 80 ° C. Most preferably, it is 35 ° C or more and 70 ° C or less. Preferred pAg is 6.5 or more and 11.5 or less. It may be preferable to use the silver halide solvent described above,
The most preferred silver halide solvent is a thiocyanate salt. In the final grain, the halogen-converted internal halo-silver chloride layer may not be confirmed by the above-described halogen composition analysis method depending on conditions such as the degree of the halogen conversion. However, dislocation lines can be clearly observed.

The method of introducing dislocation lines at any position on the main plane of the tabular grains and the method of introducing dislocation lines at any positions on the outer periphery of the tabular grains described above are appropriately combined and used. It is also possible to introduce dislocation lines.

As the silver halide emulsion which can be used in combination in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used. Preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide, or silver iodochlorobromide.

The tabular grains of the present invention are described in "Theory and Practice of Photography" by Cleve, Cleve, Photgraphy Theory and Practice.
(1930), 131; Gatov, Photographic Science and Engineering (Gutoff, Photograph
ic Science and Engineering), vol. 14, pp. 248-257 (1970); U.S. Pat.
414,310, 4,433,048, 4,4
It can be easily prepared by the methods described in JP 39,520 and British Patent 2,112,157.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H.I. Freesel (H.
Frieser), Die Grundlagen der Photographischen Prozesse
mit Selberhalogeniden (Academiche Ferragus Gesersacht 1968), pages 675 to 734.

That is, compounds containing sulfur which can react with active gelatin or silver (for example, thiosulfates, thioureas,
Sulfur sensitization using mercapto compounds, rhodanines); reduction sensitization using reducing substances (eg, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (eg, Metal sensitization method using chromium, gold complex salts, Pt, Ir, Pd and other metals of Group VIII of the periodic table, and selenium sensitization method using selenium compounds (selenoureas, selenoketones, selenides, etc.) Etc. can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. . Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl groups and sulfone groups The above heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7)
Tetraazaindenes); benzenethiosulfonic acids;
Many compounds known as antifoggants or stabilizers, such as benzenesulfinic acid; can be added.

The timing of adding these antifoggants or stabilizers is usually performed after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. That is, in the course of silver halide emulsion grain formation, even during the addition of the silver salt solution, during the period from the addition to the start of chemical ripening, during chemical ripening (during the chemical ripening time, preferably within 50% from the start,
More preferably, up to 20%).

The addition amount of the above compound used in the present invention cannot be univocally determined by the addition method or the amount of silver halide, but is preferably from 10 ^-7 mol to 10 ^-2 mol per mol of silver halide. , More preferably 10 ^-5 to 10
^-2 moles.

Gelatin is advantageously used as a preservative (bound or protective colloid) of the photographic emulsion of the present invention, 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyvinylimidazole and polyvinylpyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Phot.
Enzyme-treated gelatin as described on pages 6, 30 (1966) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are added to gelatin. What is obtained by reacting is used.

As the dispersion medium used in the present invention, specifically, RESEARCH DISCLOSUR
E) described in section IX of Volume 176, No. 17643 (December 1978).

The silver halide photographic light-sensitive material of the present invention includes general-purpose, cinema color photographic materials such as color negative films, reversal films, cinema color negative films, color positive films, cinema positive films, black-and-white negative films, and microfilms. , X-ray films and the like. Preferred are general-purpose color and black-and-white photographic photosensitive materials.

When the present invention is applied to a color light-sensitive material, it is sufficient that at least one light-sensitive layer is provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is blue light,
A unit light-sensitive layer having color sensitivity to either green light or red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally arranged in order from the support side to red color sensitivity. Layer, green color sensitive layer, and blue color sensitivity. However, even if the above installation order is reversed according to the purpose,
Also, the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.
These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE 1,121,470 or GB
As described in US Pat. No. 923,045, it is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer so that the sensitivity decreases sequentially toward the support. Also, Japanese Patent Application Laid-Open No. 57-112751
As described in JP-A Nos. 62-200350, 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / 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. Further, as described in JP-A-56-25738 and JP-A-62-63936, a blue-sensitive layer / GL is used from the side farthest from the support.
The sequences may be arranged in the order of / RL / GH / RH. Also Tokunoaki
As described in No. 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 halogen having a lower sensitivity than the middle layer. An example is an arrangement in which silver halide emulsion layers are arranged, and three layers of different sensitivities are sequentially reduced in sensitivity toward a support. Even in the case of such three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitivity emulsion layer / layer in the same color-sensitive layer from the side away from the support. They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.
The arrangement may be changed as described above even in the case of four or more layers. US 4,663,271, 4,7 to improve color reproducibility
05,744, 4,707,436, JP-A-62-160448, 63-8
It is preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in the specification of No. 9850, adjacent to or adjacent to the main photosensitive layer.

Preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. Even if the grain size of silver halide is about 0.2 μm or less, the projected area diameter is about
Large-sized grains up to 10 μm may be used, and polydisperse emulsions or monodisperse emulsions may be used. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, “I. Emulsion preparation and type
s) ”, and No. 18716 (November 1979), p. 648, N
o.307105 (November 1989), pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.Gl.
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering (Gutof)
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226; 4,414,310;
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type in which a latent image is mainly formed on the surface,
Either an internal latent image type formed inside the grains or a type having a latent image on both the surface and the inside may be used, but a negative emulsion is required. Of the internal latent image type,
The emulsion may be a core / shell type internal latent image type emulsion described in 3-264740, and its preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development process and the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat.No.4,082,553.
It is preferred to apply the silver halide grains and the colloidal silver having the inside of the grains described in No. 4852 to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. The method for its preparation is described in US Pat. No. 4,626,498, JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm
And particularly preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or the number of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferred that

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Supersensitizer-page 649, right column 4. Brightener 24, page 647, right column, page 868 5 Light absorbers, pages 25-26, page 649, right column, page 873 Filters-page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873-874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26-27 650 right column 875-876 Surfactant 9. Static 27 page 650 right column 876-877 Inhibitor 10. Matting agent 878-879

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred. Yellow coupler: a coupler represented by formulas (I) and (II) of EP 502,424A; a coupler represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); US Pat. No. 5,066,576 A coupler represented by the general formula (I) of claim 1 of US Pat.
A coupler represented by the general formula (I) on line 45 to 55 of column 1; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; described in claim 1 on page 40 of EP 498,381A1. (Especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (41)
P.)); US Pat. No. 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) (especially II-17, 19 (column 17), II
-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (lower right of page 11), L
-68 (lower right of page 12), L-77 (lower right of page 13); [A-4]-of EP 456,257
63 (p. 134), [A-4] -73, -75 (p. 139); M-4, -6 in EP 486,965
(P. 26), M-7 (p. 27); M- of paragraph 0024 of Japanese Patent Application No. 4-234120.
45; M-1 of paragraph 0036 of Japanese Patent Application No. 4-36917;
M-22 of paragraph 0237 of the issue. Cyan coupler: CX-1,3,4,5,11,1 of JP-A-4-04843
2,14,15 (pages 14 to 16); C-7,10 (35
P., 34, 35 (p. 37), (I-1), (I-17) (pp. 42-43);
The coupler represented by the general formula (Ia) or (Ib) according to claim 1 of 236333. Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11)
.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (p. 51)), the compound represented by formula (1) of Japanese Patent Application No. 4-134523 (particularly, paragraph (0027) (23)), and the compounds represented by formulas (I) and (I) described in EP 440,195A2, pp. 5-6. Compounds represented by II) and (III) (especially 29
Page I- (1)); Bleaching accelerator releasing compound: EP 310,125 A2-5
Compounds represented by formulas (I) and (I ') on page 61 (especially (6
0), (61)) and the compound represented by formula (I) of claim 1 of Japanese Patent Application No. 4-325564 (particularly, paragraph (0022) (7)); a ligand releasing compound: LIG described in claim 1 of US Pat. No. 4,555,478. A compound represented by -X (especially, a compound on lines 21 to 41 of column 12); a leuco dye-releasing compound: column 3, US 4,749,641
Fluorescent dye-releasing compound: US 4,774,181
A compound represented by COUP-DYE of claim 1 (especially compounds 1 to 11 in columns 7 to 10); a development accelerator or a fogging agent releasing compound: formulas (1), (2) in column 3 of US 4,656,123;
A compound represented by (3) (particularly (I-22) in column 25) and
ExZK-2, page 75, lines 36-38 of EP 450,637A2; Compound which releases a group which becomes a dye only after leaving: compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly, columns 25 to 36)
Y-1 to Y-19).

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
No. 15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,8
6,93 (pages 140 to 144); Latex for impregnation of oil-soluble organic compound: latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: Represented by formula (I) in columns 2 to 54 to 62 of US 4,978,606. Compounds (especially I-, (1), (2), (6), (1
2) (Columns 4-5), 5-1 of Column 2 of US 4,923,787
Line 0 formula (especially compound 1 (column 3); stain inhibitor:
Formulas (I) to (III) on page 4, lines 30 to 33 of EP 298321A, especially I-47,
72, III-1, 27 (pages 24 to 48); Anti-fading agent: EP 298321A A
-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,
164 (pp. 69-118), US 5,122,444, columns 25-38 II-1
~ III-23, especially III-10, I-1 on pages 8 to 12 of EP 471347A ~
III-4, especially II-2, A-1, from columns 32 to 40 of US 5,139,931
48, especially A-39, 42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II on pages 5 to 24 of EP 411324A
-15, especially I-46; Formalin Scavenger: EP 477932A
SCV-1 to 28 on page 24 to 29, especially SCV-8; hardener:
Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1,4,6,8,14, US 4,618,573 on page 17 of 1-214845 (H-1 to
54), a compound (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, especially claim 1 of H-14, US 3,325,287
Compounds described in the above; Development inhibitor precursor: JP-A-62-1
No. 68139, P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, in particular, columns 28, 29; preservatives, fungicides: columns 3, 15 of US 4,923,790 I-1 to III-
43, especially II-1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially I-
1,60, (2), (13), US Pat. No. 4,952,483, Compounds 1-65, especially 36, in columns 25-32: Chemical sensitizer: Triphenylphosphine selenide, Compound 50 of JP-A-5-40324; Dye: JP-A-3-156450 a-1 to b-20 on pages 15 to 18, especially a-1, 12, 18,
27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, EP 4456
FI-1 to F-II-43 on pages 33 to 55 of 27A, especially FI-11, F-II-8,
III-36 on pages 17-28 of EP 457153A, especially III-1,3, W
O88 / 04794 Microcrystal dispersion of 8-26 Dye-1 to 124, EP
Compounds 1 to 22 on pages 6 to 11 of 319999A, especially compound 1, EP
Compounds D-1 to 519306A represented by formulas (1) to (3)
87 (pages 3 to 28), compounds 1 to 22 represented by formula (I) of US 4,268,622 (columns 3 to 10), and compounds (1) to (31) represented by formula (I) of US 4,923,788 (column 2 To 9); UV absorber: compounds (18b) to (1) represented by formula (1) of JP-A-46-3335.
8r), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 represented by formula (III) in EP 520938A. 10 (page 14), Equation (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. It is also suitable for a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784. Suitable supports that can be used in the present invention are described in, for example, RD. No.17643, page 28, No.18716
No. 307105 No. 8 from the right column on page 647 to the left column on page 648
It is described on page 79. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less,
It is more preferably at most 18 μm, particularly preferably at most 16 μm. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is 30 ° C., 3
When 90% of the maximum swelling film thickness reached when the treatment is performed for 15 minutes is defined as the saturated film thickness, it is defined as the time until the film thickness reaches half. The film thickness is controlled at 25 ° C and 55% relative humidity (2 days)
T _1/2 is the thickness of the film measured by A. Green et al. (Photogr.Sci.Eng.), 19, 2,
It can be measured by using a serometer (swelling meter) of the type described on pages 124-129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the following formula:
It can be calculated by (maximum swollen film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber,
It is preferable to include an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention can be prepared according to the RD. No.176
No. 18716, No. 18716, left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development processing. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used.Typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor or an antifoggant such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts are added.

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions 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 the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The processing effect due to the contact between the photographic processing liquid and the air in the processing tank is determined by the aperture ratio (= [contact area between the processing liquid and the air].
cm ² ] ÷ [volume of treatment liquid cm ³ ]). This aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, JP-A-63-216050 And the slit developing method described in the above item. The aperture ratio is preferably reduced not only in both the color development and black-and-white development steps but also in the following various steps, for example, in all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Also,
By using means for suppressing the accumulation of bromide ions in the developer, the amount of replenishment can be reduced. The time of the color development processing is usually set between 2 and 5 minutes.
By setting the pH and the color developing agent at a high concentration, the processing time can be further reduced.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid Etc. can be used. Among these, iron (III) aminopolycarboxylates including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex
Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: US 3,893,858, DE 1,290,812, JP 2,059,988, JP-A-53-32736, JP-A 53-57831, JP-A 53-37418, 53-7
No. 2623, No. 53-95630, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623, No. 53-28426,
Compounds having a mercapto group or disulfide group described in RD No. 17129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; Japanese Patent Publication No. 45-8506;
Nos. 52-20832, 53-32735, and thiourea derivatives described in US Pat. No. 3,706,561; DE 1,127,715, iodide salts described in JP-A-58-16235; and polyoxyethylene compounds described in DE 966,410 and 2,748,430 Polyamine compounds described in JP-B-45-8836; and JP-A-49-40943, JP-A-49-59644, and
53-94927, 54-35727, 55-26506, 58-16394
Compounds described in No. 0; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferable in view of a large accelerating effect, and particularly, US 3,893,858,
Compounds described in DE 1,290,812 and JP-A-53-95630 are preferred. Further, compounds described in US Pat. No. 4,552,834 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 photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain, in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (p
Ka) is a compound having 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodides, and thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, or thiourea. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294769A is preferable. Furthermore, aminopolycarboxylic acids or 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, a fixing solution or a bleach-fixing solution contains p for adjusting pH.
Compound having Ka of 6.0 to 9.0, preferably imidazole, 1-
Imidazoles such as methylimidazole, 1-ethylimidazole and 2-methylimidazole are added in an amount of 0.1 ml / liter.
It is preferable to add 1 to 10 mol.

It is preferable that the total time of the desilvering step is shorter as long as defective desilvering does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

Automatic developing machines used for the light-sensitive material of the present invention are described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-1912.
It is preferable to have the photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. This is particularly effective in reducing the processing time and reducing the replenishing amount of the processing solution.

The light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of t
he Society of MotionPicture and Television Enginee
rs Volume 64, pages 248 to 253 (May, 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but bacteria increase due to the increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this, a method of reducing calcium ions and magnesium ions described in JP-A-62-288838 is extremely effective. Also, chlorine fungicides such as isothiazolone compounds, thiabendazoles, chlorinated sodium isocyanurate and the like described in JP-A-57-8542, other benzotriazoles, Hiroshi Horiguchi, "Chemistry of fungicides and fungicides". (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

In the processing of the light-sensitive material of the present invention, washing water
The pH is between 4 and 9, preferably between 5 and 8. Washing water temperature and washing time can also be set according to the characteristics and application of the photosensitive material, but are generally 20 to 10 minutes at 15 to 45 ° C, preferably 25 to 45 ° C.
A range of 30 seconds to 5 minutes at 4040 ° C. is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be applied.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, a stabilization bath containing a dye stabilizer and a surfactant used as a final bath of a color photographic light-sensitive material for photography may be used. Can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use a precursor of a color developing agent. For example, US 3,34
Indaniline compounds described in 2,597, 3,342,599,
Research Disclosure No.14850 and No.15159
Schiff base type compound described, aldol compound described in JP 13,924, metal salt complex described in US 3,719,492, JP-A-53-1
The urethane compounds described in 35628 can be mentioned. The light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339,
Nos. 57-144547 and 58-115438. The processing solution used for processing the photosensitive material of the present invention is 10 ° C.
Used at 5050 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can improve the image quality and improve the stability of the processing solution. it can.

There are no particular restrictions on the various additives and development methods used when the present invention is applied to black-and-white photographic materials. For example, JP-A-2-68539 and JP-A-5-11389.
And Japanese Patent Application Laid-Open No. 2-58041 can be preferably used.

[0273] 1. Silver halide emulsion and method for producing the same
From page 6, lower right column, line 6 to page 10, upper right column, line 12 of JP-A-2-68539. 2. Chemical sensitization method: page 10, top right column, line 13 to bottom left column, 16
Line, selenium sensitization method described in JP-A-5-11389. 3. Antifoggant / stabilizer: JP-A-2-68539, No. 10
Line 17 in the lower left column of the page to line 7 in the upper left column of the page 11, and line 2 in the lower left column of the page 3 to the lower left column of the page 4. 4. Spectral sensitizing dye: page 4, lower right column, line 4 to page 8, lower right column, and JP-A-2-58041, page 12, lower left column, line 8 to line 19, lower right column. 5. Surfactant / antistatic agent: Japanese Patent Laid-Open No. 2-68539 No. 1
Line 14 from the upper left column on page 1 to line 9 from the upper left column on page 12 and JP-A-2-5
8041, page 2, lower left column, line 14 to page 5, line 12. 6. Matting agent, plasticizer, slip agent: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eye. 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16; 8. Hardener: page 12, lower left column, line 17 to page 13, upper right column 6,
Line. 9. Developing method: same as page 15, upper left column, line 14 to lower left column 13,
Line.

Further, the silver halide light-sensitive material of the present invention is a US silver halide light-sensitive material.
4,500,626, JP-A-60-133449, JP-A-59-218443,
The invention can also be applied to photothermographic materials described in JP-A-61-238056 and EP 210,660A2.

The silver halide light-sensitive material carrying magnetic recording that can be used in the present invention may be any material having a magnetic recording layer. The magnetic recording layer is provided adjacent to the support or provided via another photographic component layer. The above-mentioned magnetic recording layer is disclosed in
4642 and a stripe shape described in JP-A-4-124645. As the magnetic recording layer, JP-A-59-2
3505, JP-A-4-195726, JP-A-6-593
57 can be applied. The silver halide emulsion used here is described in JP-A-4-166932.
JP-A-3-41436 and JP-A-3-41437 can be used.

As the support, triacetate cellulose and polyethylene terephthalate which are transparent and have been conventionally used for color films can be used. Preferably, a polyethylene aromatic dicarboxylate polyester support is used. It is preferable from the viewpoint of magnetic recording characteristics. Among the polyethylene aromatic dicarboxylate-based polyester supports, polyethylene naphthalate is particularly preferred. The thickness of the support is from 50 μm
300 µm, preferably 50 µm to 200 µm, more preferably 80 to 115 µm, particularly preferably 85 to 10
5 μm. As the support, JP-A-6-3511
8, JP-A-6-17528, Invention Association published technical report 94-6
Preference is given to a thin-layer support of a pre-heat-treated polyester as described in detail at 023. Specifically, a material that has been heat-treated (annealed) at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 1 to 1500 hours is preferable. In addition to the above support,
UV irradiation described in JP-B-43-2603, JP-B-43-2604 and JP-B-45-3828, JP-B-48-504
3, corona discharge described in JP-A-51-131576, etc.
A surface treatment such as a glow discharge described in JP-B-35-7578 and JP-B-46-43480, and US Pat.
No. 89, and if necessary, U.S. Pat.
761, 791 may be provided, and if necessary, an antistatic treatment described in JP-A-4-62543 may be performed.

The light-sensitive material made in this way is Japanese Patent Publication No. 4-86817.
It is preferable to manufacture according to the manufacturing control method described in the description, and record the manufacturing data by the method described in JP-B-6-87146. After or before, according to the method described in JP-A-4-125560, the film is cut into a narrower film than the conventional 135 size, and the perforations are reduced to match the small format screen smaller than the conventional one. Perforate two holes per side. The film thus obtained is a cartridge package of Japanese Patent Application Laid-Open No. 4-157559, a cartridge shown in FIG. 9 of an embodiment of Japanese Patent Application Laid-Open No. 5-210202, or a film cartridge of U.S. Pat. No. 4,221,479 or U.S. Pat. 308, US Pat. No. 4,834,366, US Pat. No. 5,226,61
3. It can be used in the cartridge described in U.S. Pat. No. 4,846,418. As the film cartridge or film cartridge used here, a type capable of accommodating a tongue as described in U.S. Pat. No. 4,848,893 and U.S. Pat. No. 5,317,355 is preferable from the viewpoint of light shielding properties.

Further, US Pat. No. 5,296,886
A cartridge having a lock mechanism such as described above, a cartridge displaying a use state described in US Pat. No. 5,347,334, and a cartridge having a double exposure prevention function are preferable. Further, as described in JP-A-6-85128, a cartridge to which a film can be easily mounted simply by inserting a film into the cartridge may be used. The film cartridge made in this way is photographed, developed and processed using a camera, developing machine, and laboratory equipment described below.
It can be used for various ways of enjoying photos.

For example, JP-A-6-8886, JP-A-6-8866
Japanese Patent Application Laid-Open No. 6-5 / 99908
7398, an automatic winding camera described in JP-A-6-101135, a camera described in JP-A-6-205690, which can take out and replace the type of film during photographing, and a camera described in JP-A-5-101690.
-293138 and Japanese Patent Application Laid-Open No. 5-283382, for example, a camera capable of magnetic recording on a film a panoramic image, a high-vision image, and a normal image (magnetic recording capable of selecting a print aspect ratio). The function of a film cartridge (patrone) can be sufficiently exhibited by using a camera having a double exposure prevention function described in JP-A-101194 or a camera having a use state display function such as a film described in JP-A-5-150577.

The film photographed in this way is processed by a self-developing machine described in JP-A-6-222514 and JP-A-6-222545, or before, during or after the processing, as disclosed in JP-A-6-95265. The method of utilizing magnetic recording on a film described in Japanese Unexamined Patent Application Publication No. Hei 4-123054 may be used, or the aspect ratio selection function described in Japanese Patent Application Laid-Open No. Hei 5-19364 may be used. In the case of cine-type development during development processing,
And splicing according to the method described in -119461.
Further, when or after the development processing,
5. Attach and detach processing described in 5. After processing in this manner, Japanese Patent Application Laid-Open Nos. 2-184835 and 4-1863.
35, film information may be converted to print through back printing and front printing on color paper by the method described in JP-A-6-79968. Further, it may be returned to the customer together with the index print and return cartridge described in JP-A-5-11353 and JP-A-5-232594.

[0281]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A finished emulsion obtained by mixing an emulsion and an emulsion containing a coupler was prepared and coated to show the effect of the present invention on the stability over time of the finished emulsion. (Preparation of seed emulsion a) KBr 4.5 g, average molecular weight 150
1600 ml of an aqueous solution containing 7.9 g of gelatine
The mixture was kept at 0 ° C and stirred. AgNO ₃ (8.9 g) aqueous solution and K
An aqueous solution of KBr (6.2 g) containing 6.3% by weight of I was added by a double jet method over 40 seconds. Gelatin 38
After the addition of g, the temperature was raised to 58 ° C. AgNO ₃ (5.
6 g) After the aqueous solution was added, 0.1 mol of ammonia was added, and after 15 minutes, the mixture was neutralized with acetic acid to adjust the pH to 5.0. A
An aqueous gNO ₃ (219 g) solution and an aqueous KBr solution were added over 40 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was set to -10 with respect to the saturated calomel electrode.
mV. After desalting, add 50 g of gelatin and add
The pH was adjusted to 5.8 and the pAg was adjusted to 8.8 at ℃ to prepare a seed emulsion a. This seed emulsion contained 1 mol of Ag per 1 kg of emulsion,
Contains 80g of gelatin, average circle equivalent diameter 0.62μ
m, coefficient of variation of equivalent circle diameter 16%, average thickness 0.103
These were tabular grains having an average aspect ratio of 6.0 μm. (Preparation method of emulsion A) 134 g of seed emulsion a, 1.9 KBr
g and 38 g of gelatin in an aqueous solution (1200 ml) were stirred at 78 ° C. After adding 2 mg of thiourea dioxide, Ag
An aqueous solution of NO ₃ (87.7 g) and an aqueous KBr solution containing 17.9% by weight of KI were added over 46 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -40 mV with respect to the saturated calomel electrode. Then, AgNO ₃
(42.6 g) Aqueous solution and KBr aqueous solution were added by a double jet method over 17 minutes. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. The silver potential was adjusted to -80 mV by adding 44 mg of sodium ethylthiosulfonate and an aqueous KBr solution. Average circle equivalent diameter 0.025μ
After rapidly adding 7.1 g of a silver iodide fine grain emulsion having a coefficient of variation of m and a circle equivalent diameter of 18% within 5 seconds in terms of AgNO ₃ amount, 30 seconds later, an aqueous solution of AgNO ₃ (66.4 g) was added for 8 minutes. Over a period of time. The silver potential after the addition was -10 mV. Perform normal water washing, add gelatin, and add
The pH was adjusted to 5.8 and pAg to 8.8. This emulsion was designated as emulsion A.

Emulsion A was tabular grains having an average equivalent circle diameter of 1.17 μm, a coefficient of variation of the equivalent circle diameter of 26%, an average thickness of 0.23 μm, an average aspect ratio of 5.1, and an average equivalent sphere diameter of 0.78 μm. Grains having an aspect ratio of 5 or more accounted for 60% or more of the total projected area. Emulsion A was heated to 60 ° C., and the following sensitizing dye, potassium thiocyanate, chloroauric acid,
Sodium thiosulfate, N, N-dimethylselenourea and the compounds of the present invention were added as shown in Table 1 and optimally sensitized.

[0284]

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[0285]

[Table 1]

(Preparation of emulsion containing coupler) 10.6 g of the following compound as a magenta coupler was dissolved in 11 ml of tricresyl phosphate and 30 ml of ethyl acetate.
It was mixed with 200 ml of an aqueous gelatin solution and emulsified and dispersed in a colloid mill.

[0287]

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In the preparation of the above emulsion, an emulsion in which the compound of the present invention was dissolved and emulsified and dispersed together with a magenta coupler was prepared in the same manner to obtain the emulsion shown in Table 2.

[0289]

[Table 2]

The emulsions shown in Table 1 and the emulsions shown in Table 2 were mixed and stirred at 40 ° C. to obtain a finished emulsion. The finished emulsions aged for 1 hour and those aged for 6 hours were coated on a cellulose triacetate acetate film support under the coating conditions shown in Table-3.

[0291]

[Table 3]

These samples were left under the conditions of 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was carried out for 1/100 second through a continuous wedge with a gelatin filter SC-50 manufactured by Fuji Photo Film Co., Ltd.

Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., processing was performed by the method described below (until the cumulative replenishment amount of the solution became three times the mother liquor tank capacity). (Processing method) Process Processing time Processing temperature Refill Amount of color development 3 minutes 15 seconds 38 ° C 45 ml Bleaching 1 minute 00 seconds 38 ° C 20 ml The entire amount of bleaching liquid flows into the bleach-fix tank Bleach-fix 3 minutes 15 seconds 38 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping method from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30 ml Stabilized 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ° C * Replenishment amount per 35 mm width and 1.1 m length (corresponding to 24 Ex. 1 line) Next, the composition of the processing solution is described. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid) 10.05 10.10 (Bleaching solution) Common to tank solution and replenisher (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH _{3) 2 N-CH 2 -CH} 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 ml PH 1.0 (adjusted with aqueous ammonia and nitric acid) 6.3 (Bleaching / fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous solution of ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 7.2 7.3 (Wash solution) A mixed-bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water and the concentration of calcium and magnesium ions is 3 mg / liter or less. Treated, followed by the addition of sodium isocyanurate dichloride 20mg / liter and sodium 0.15 g / l of sulfuric acid. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added thereto, and the concentration of a sample treated with 1.0 liter and pH 8.5 was measured with a green filter. The results obtained are shown in Table 4 below. The sensitivity is fog density plus 0.
The values were expressed as relative values of 2 and 1.5.

[0294]

[Table 4]

The difference in sensitivity was determined by measuring the density of a sample obtained by aging the completed emulsion for 6 hours at the same exposure as that giving a density of (fog +1.5) in the sample obtained by aging the completed emulsion for 1 hour. Was calculated and described in the table. As is clear from Table 4, the emulsion to which only the compound represented by the general formula (S1) is added tends to increase the fog as the time required for coating the finished emulsion increases. Emulsions to which only the compound represented by the general formula (S2) is added also tend to have an increase in fog as the time required for coating the finished emulsion increases. However, the finished emulsion prepared by mixing the emulsion to which the compound represented by the general formula (S1) is added and the emulsion to which the compound represented by the general formula (S2) is added is extremely photographic regardless of the aging time until coating. It turned out that the performance was stable. Furthermore, the general formula (S
When the compound represented by the general formula (XVIII) among the compounds represented by 1) and the compound represented by the general formula (S4) among the compounds represented by the general formula (S2) were used (Sample Nos. 3, 4) , 14, 15 and 16) It is also clear that stabilization of the photographic properties has been remarkably achieved.

Example 2 On a cellulose triacetate film support having an undercoat, various layers having the following compositions were applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M silver 0.065 ExC-2 0.04 polyethyl acrylate latex 0.20 gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide 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-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E silver 0.15 silver iodobromide emulsion F silver 0.10 silver iodobromide emulsion G silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.015 Cpd-1 0.16 solid disperse dye ExF-5 0.060 solid disperse dye ExF-6 0.060 oil-soluble dye ExF-7 0.010 HBS-1 0.60 gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

Fourteenth layer (second protective layer) Silver iodobromide emulsion M silver 0.10 H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, W-1 to W-3, B-4 to B- are preferably added to each layer to improve the storability, processability, pressure resistance, fungicidal / bacteriostatic, antistatic and coating properties. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains palladium, iridium and rhodium salts.

[0312]

[Table 5]

In Table 5, (1) Emulsions J to L were prepared according to the examples of JP-A-2-19938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

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

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

[0316]

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[0317]

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[0318]

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[0319]

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[0320]

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[0321]

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[0322]

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[0323]

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[0324]

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[0325]

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[0326]

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[0327]

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[0328]

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[0329]

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[0330]

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[0331]

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Next, the compound (S1-19) represented by the general formula (S1) of the present invention was added to the emulsions D, H and L of the sample 101 at 4.5 × 10 ^-6 mol per mol of silver halide. Sample 102 was prepared in exactly the same manner except that the compound represented by the general formula (S2) was added to the fifth, eighth, and twelfth layers at 0.03 g / m ² . Further, a sample 103 was prepared in exactly the same manner as the sample 102 except that (S1-52) was used instead of (S1-19) used in the sample 102. After exposing the obtained samples 102 and 103 to 60 ° C.-6
After exposing for 1 day under 0% condition, it was left for 1 day at room temperature.
After a total of 10 days, this combination was treated with a running solution using the following sample 101. Samples 102 and 103 showed a small change in photographic properties as compared with the sample treated immediately after exposure. Met.

Next, after exposing the sample 101, using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd.
The treatment was carried out in the manner described below (until the cumulative replenishment amount of the liquid became three times the volume of the mother liquor tank). (Processing method) Process Processing time Processing temperature Refill Amount of color development 3 minutes 15 seconds 38 ° C 45 ml Bleaching 1 minute 00 seconds 38 ° C 20 ml The entire amount of bleaching liquid flows into the bleach-fix tank Bleach-fix 3 minutes 15 seconds 38 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping method from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30 ml Stabilized 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ° C * Replenishment amount per 35 mm width and 1.1 m length (corresponding to 24 Ex. 1 line) Next, the composition of the processing solution is described. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid) 10.05 10.10 (Bleaching solution) Common to tank solution and replenisher (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH _{3) 2 N-CH 2 -CH} 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 ml PH 1.0 (adjusted with aqueous ammonia and nitric acid) 6.3 (Bleaching / fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous solution of ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 7.2 7.3 (Wash solution) A mixed-bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water and the concentration of calcium and magnesium ions is 3 mg / liter or less. Treated, followed by the addition of sodium isocyanurate dichloride 20mg / liter and sodium 0.15 g / l of sulfuric acid. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water and add 1.0 liter pH 8.5

[0334]

The silver halide photographic light-sensitive material of the present invention is excellent in raw storability and latent image storability, and has high stability under production conditions.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mamoru Sakurazawa 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A compound represented by the following general formula (S1)
Containing at least one and represented by the following general formula (S2)
Characterized in that it contains at least one compound
Silver halide photographic material. Embedded imageIn the general formula (S1), Het is an adsorptive group to silver halide.
is there. However, the group represented by Het includes at least one
-(Q) k2-(Hy) in the above is substituted. Q is a carbon source
Atom, nitrogen atom, sulfur atom and oxygen atom
Shows a divalent linking group consisting of one or more atoms or atomic groups
I forgot. Hy is a hydrazine structure represented by the following general formula (II)
Represents a group having a structure. Embedded imageIn the formula (II), R₁₁, R₁₂, R₁₃And R₁₄Are each aliphatic
Group, an aryl group or a heterocyclic group,₁₁And R₁₂, R
₁₃And R₁₄, R₁₁And R₁₃Or R₁₂And R₁₄Are connected to each other
To form a ring. Where R₁₁, R₁₂, R₁₃Passing
And R₁₄At least one of-in the general formula (S1)
(Q)_k2-(Het)_k1Is a divalent aliphatic for substitution
Group, an aryl group or a heterocyclic group. k1 and k3 are
Each represents 1, 2, 3 or 4, and k2 represents 0 or 1.
You. Embedded imageIn the general formula (S2), R₆₁Represents an aliphatic group, an aryl group,
Group, alkyl or arylsulfonyl group, alkyl
Or arylsulfinyl group, carbamoyl group, sulf
Famoyl group, alkoxycarbonyl group or aryl
Represents an oxycarbonyl group;₆₂Is a hydrogen atom or R₆₁
Represents a group having the same meaning as the group shown by. Where R ₆₁Is an aliphatic group
Or an aryl group, R₆₂Is an acyl group, alkyl or
Arylsulfonyl group, alkyl or arylsulf
Ynyl group, carbamoyl group, sulfamoyl group, alcohol
Xycarbonyl group or aryloxycarbonyl group
is there. R₆₁And R₆₂Combine with each other to form a 5- to 7-membered ring
May be.