JP2003149774A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, excellent in antistatic performance and less liable to variation of fog due to processing. SOLUTION: In the silver halide photographic sensitive material having on the base at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer, at least one selected from the group of the compounds of formulae (A)-(G) is contained and at least one of the compounds of formula (I) is also contained. In the formulae, each substituent is defined as described in the specification.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity, excellent antistatic properties and small fog variation due to processing. Is.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials, higher sensitivity is required more and more in order to enhance user's benefit, and in recent years, remarkable sensitivity enhancement has been achieved by enormous research on high sensitivity. In order to increase the sensitivity of silver halide light-sensitive materials, it is very important to increase the sensitivity specific to silver halide grains, and various methods are used to increase the sensitivity specific to silver halide grains. Has been. For example, sensitization by chemical sensitizers such as sulfur, gold and Group VIII metal compounds, and chemical sensitizers such as sulfur, gold and Group VIII metal compounds and additives that promote their sensitizing effect. High sensitivity due to combination,
Further, the sensitivity is increased by adding an additive having a sensitizing effect depending on the type of silver halide emulsion. Regarding these, for example, Research Disclosure, 120
Volume, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361 and 3,297,44.
No. 6, No. 3,772,031, No. 3,857,7
11, No. 3,901,714, No. 4,266,0
18 and 3,904,415, and British Patent 1,315,755. Further, a method of reducing and increasing silver halide grains is also used as a means for increasing sensitivity. Regarding reduction sensitization of silver halide grains, see US Pat. No. 2,518,698.
No. 3, No. 3,201,254, No. 3,411,91
No. 7, No. 3,779, 777, No. 3,930, 8
No. 67, and the method of using the reducing agent is described in, for example, JP-B-57-33572 and 58-141.
0, JP-A-57-179835. Also, recently, U.S. Pat. Nos. 5,747,235, 5,747,236, European Patents 786692A1, 893731A1, 893732A1, and WO9.
A sensitization technique using an organic electron-donating compound composed of an electron-donating group and a leaving group as described in 9/05570 has been reported. This method is an unprecedented new sensitization technique and is effective for increasing the sensitivity.

On the other hand, a photographic light-sensitive material comes into contact with various substances during its manufacturing, photographing and developing processes. For example, in the processing step, when the photosensitive material is in a wound state, the back layer formed on the back surface of the support may come into contact with the surface layer. Further, it may come into contact with stainless steel, a rubber roller, or the like when it is transported in the processing step. When contacted with these materials, the surface of the photosensitive material (gelatin layer) is likely to be positively charged, and in some cases causes unnecessary discharge, leaving undesired exposure marks (called static marks) on the photosensitive material. It will be. A compound having a fluorine atom is effective for reducing the chargeability of gelatin, and a fluorine-based surfactant is often added. In recent years, it has become more and more important to increase the transfer speed in order to improve the productivity of the manufacturing process and the developing process, and to improve the charging characteristics by the high-speed transfer of the camera. As described above, the fluorine-based surfactant is used as a material having a function of imparting antistatic property to the photographic light-sensitive material, and is disclosed in, for example, JP-A-49-46733, JP-A-51-32322, and JP-A-57-322. No. 64228, No. 64-536, No. 2-141739, No. 3-95550.
Specific examples thereof are disclosed in Japanese Laid-Open Patent Publication No. 4-248543 and the like. However, these materials do not always have satisfactory performance in response to the recent demands for higher sensitivity, higher speed coating and higher speed conveyance of photographic light-sensitive materials.

Further, it has been found that the variation in fog caused by the development process may become large in combination with the above-mentioned sensitization technique using an organic electron-donating compound, and improvement of the fluorine-containing surfactant has been desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent antistatic properties, and less fog variation due to processing.

[0006]

The objects of the present invention have been achieved by the following method. (1) In a silver halide color photographic light-sensitive material having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, the following general formula ( At least one compound selected from the group consisting of compounds represented by general formula (G) to A) and represented by general formula (I) below.
A silver halide color photographic light-sensitive material containing a seed.

General formula (A)

[Chemical 11]

In the formula, RED ₁₁ represents a reducing group, L ₁₁ represents a leaving group, and R ₁₁₂ represents a hydrogen atom or a substituent.
R ₁₁₁ together with the carbon atom (C) and RED ₁₁ can form a cyclic structure corresponding to a tetrahydro body, hexahydro body, or octahydro body of a 5- or 6-membered aromatic ring (including aromatic heterocycle). Represents a metal atomic group.

General formula (B)

[Chemical 12]

In the formula, RED ₁₂ and L ₁₂ each represent a group having the same meaning as RED ₁₁ and L _{11 in} formula (A). R
₁₂₁ and R ₁₂₂ each represent a substituent capable of substituting for a hydrogen atom or a carbon atom, which is represented by R _{112 of the} general formula (A).
Is a group of the same meaning. ED ₁₂ represents an electron donating group. In the general formula (B), R ₁₂₁ and RED ₁₂ , R ₁₂₁ and R ₁₂₂ , or ED ₁₂ and RED ₁₂ may combine with each other to form a cyclic structure.

General formula (C)

[Chemical 13]

In the formula, RED ₂ has the same meaning as RED _{12 in} formula (B). L ₂ represents a carboxy group or a salt thereof, and R ₂₁ and R ₂₂ represent a hydrogen atom or a substituent. RED
₂ and R _{2 1} may combine with each other to form a ring structure. However, the compound represented by the general formula (C) is a compound having two or more adsorption promoting groups for silver halide in the molecule.

General formula (D)

[Chemical 14]

Where RED₃Is RED of general formula (B)₁₂When
Represents a synonymous group. Y₃Is RED₃Is 1 electron oxidized and raw
React with the formed one-electron oxidant to form a new bond
Carbon-carbon double bond site or carbon-carbon triple bond part
Represents a reactive group containing a position. L ₃Is RED₃And Y₃Concatenate with
Represents a connecting group.

General formula (E)

[Chemical 15]

In the formula, RED ₄₁ is the RED _{12 of the} general formula (B).
Represents a group synonymous with. R _{40 to} R ₄₄ each represent a hydrogen atom or a substituent.

General formula (F)

[Chemical 16]

In the formula, RED ₄₂ is RED _{12 of the} general formula (B).
Represents a group synonymous with. R _{45 to} R ₄₉ each represent a hydrogen atom or a substituent. Z ₄₂ is -CR ₄₂₀ R _421- , -NR
₄₂₃ represents-, or -O-. Here, R ₄₂₀ and R ₄₂₁ are
Each represents a hydrogen atom or a substituent, and R ₄₂₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

General formula (G)

[Chemical 17]

In the formula, RED ₀ represents a reducing group, L ₀ represents a leaving group, and R ₀ and R ₁ represent a hydrogen atom or a substituent. RED ₀ and R ₀ , and R ₀ and R ₁ may combine with each other to form a ring structure.

General formula (I)

[Chemical 18]

In the formula, R ²¹ represents a substituted or unsubstituted alkyl group, and R _af represents a perfluoroalkylene group. W
² represents a hydrogen atom or a fluorine atom, and La represents _a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. One of A ² and B ² is a hydrogen atom,
Other represents -L _b -SO ₃ M, M represents a cation. L _b represents a single bond or a substituted or unsubstituted alkylene group.

(2) The silver halide color photographic light-sensitive material as described in (1), wherein the compound of the general formula (I) is represented by the following general formula (Ia). General formula (Ia)

[Chemical 19]

In the formula, R ²² represents a substituted or unsubstituted alkyl group having a total carbon number of 6 or more, but R ²² is not an alkyl group substituted with a fluorine atom. R _f represents a perfluoroalkyl group having 6 or less carbon atoms, one of X ²¹ and X ²² represents a hydrogen atom and the other represents SO ₃ M, and M represents a cation. n represents an integer of 1 or more.

(3) R _f in the general formula (Ia)
Is a perfluoroalkyl group having 2 to 4 carbon atoms, and the silver halide color photographic light-sensitive material according to (2) is characterized.

(4) In the above general formula (Ia), n is 1 or 2, (2) or (3)
A silver halide color photographic light-sensitive material described in 1.

(5) A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, It contains at least one compound selected from the group of compounds represented by formulas (A) to (G) described in (1), and at least one compound represented by the following formula (II). Characteristic silver halide color photographic light-sensitive material. General formula (II)

[Chemical 20]

In the formula, A ³ and B ³ each independently represent a fluorine atom or a hydrogen atom. a and b each independently represent an integer of 1 to 6. c and d each independently represent an integer of 4 to 8. x represents 0 or 1. M represents a cation.

(6) The silver halide color photographic light-sensitive material described in (5), wherein the compound of the general formula (II) is represented by the following general formula (II-a). General formula (II-a)

[Chemical 21]

In the formula, a and b are each independently 1 to 6
Represents the integer. c and d each independently represent an integer of 4 to 8. x represents 0 or 1. M represents a cation.

(7) The silver halide color photographic light-sensitive material described in (5), wherein the compound of the general formula (II) is represented by the following general formula (II-b). General formula (II-b)

[Chemical formula 22]

In the formula, a ¹ represents an integer of 2 to 3. c ¹
Represents an integer of 4 to 6. x represents 0 or 1. M
Represents a cation.

(8) A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, Containing at least one compound selected from the group of compounds represented by formulas (A) to (G) described in (1) and containing at least one compound represented by the following formula (III): Characteristic silver halide color photographic light-sensitive material. General formula (III)

[Chemical formula 23]

In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, and at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom. R
³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, X ⁴¹ , X ⁴² and Z each independently represent a divalent linking group, and M ⁺ represents a cationic substituent. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1.

(9) The silver halide color photographic light-sensitive material described in (8), wherein the compound of the general formula (III) is represented by the following general formula (III-a). General formula (III-a)

[Chemical formula 24]

Where R¹¹And R⁴¹Respectively replace or
Represents an unsubstituted alkyl group, but R ¹¹And R⁴¹Little
At least one represents an alkyl group substituted with a fluorine atom.
And R ¹¹And R⁴¹Has a total carbon number of 19 or less.
R¹³, R¹⁴And R¹⁵Are independently replaced or absent
A substituted alkyl group, any two of which are bonded to each other
It may form a ring. X⁴¹And X⁴²Each is German
Vertically -O-, -S- or -NR³¹Represents-, R³¹Is water
It represents an elementary atom or a substituent, and Z represents a divalent linking group.
Y^-Represents a counter anion, but when the charge is zero in the molecule
If Y^-It does not have to be.

(10) The silver halide color photographic light-sensitive material described in (8), wherein the compound of the general formula (III) is represented by the following general formula (III-c). General formula (III-c)

[Chemical 25]

In the formula, n ¹ is an integer of ¹ to 6 and n ² is 3 to 8.
2 (n ¹ + n ² ) is 19 or less.
R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group, and any two of them may be bonded to each other to form a ring. X ⁴³ and X ⁴⁴ are each independently -O -, - S- or -NR ³¹ - represents, R ³¹ represents a hydrogen atom or a substituent, Z represents a divalent linking group.
Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule.

[0039]

Embodiments of the photographic light-sensitive material of the present invention are arbitrary, and the application to any color photographic light-sensitive material regardless of positive type or negative type is effective. Next, the compounds represented by formulas (A) to (G) of the present invention will be described. The sensitization technique using the organic electron donating compound used in the present invention is achieved by the following compounds of types 1 to 5.

(Type 1) The one-electron oxidant produced by one-electron oxidation is further converted into a two-electron oxidant with further bond cleavage reaction.
A compound that can emit more electrons than electrons. (Type 2) One-electron oxidant produced by one-electron oxidation is
A compound which is capable of releasing yet another electron with the subsequent carbon-carbon bond cleavage reaction and which has two or more groups capable of adsorbing silver halide in the same molecule. (Type 3) One-electron oxidant produced by one-electron oxidation is
A compound capable of further emitting one or more electrons after the subsequent bond formation process. (Type 4) One-electron oxidant produced by one-electron oxidation
A compound capable of further releasing one or more electrons after undergoing a ring-opening reaction in the molecule. (Type 5) In the compound represented by XY, X represents a reducing group, Y represents a leaving group, and the reducing group represented by X is one-electron oxidized to form a one-electron oxidant, Continued XY
A compound capable of leaving Y along with a bond cleavage reaction to generate an X radical, and further releasing another electron therefrom.

Among the compounds of types 1 to 5 above, the preferred one is "a compound having an adsorptive group for silver halide in the molecule" or "a partial structure of the spectral sensitizing dye in the molecule. Having a compound ”. More preferably "a compound having an adsorptive group for silver halide in the molecule"
Is.

The compounds of types 1 to 5 will be described in detail. In the compound of type 1, "bond cleavage reaction" specifically means the cleavage of carbon-carbon or carbon-silicon bond, and the cleavage of carbon-hydrogen bond may be accompanied. The compound of type 1 is oxidized by one electron to form a one-electron oxidant, and then the bond cleavage reaction is performed for the first time.
It is a compound capable of emitting electrons of electrons or more (preferably 3 or more electrons). In other words, it is a compound that can be further oxidized by 2 or more electrons (preferably 3 or more electrons).

Among the compounds of type 1, preferred compounds are represented by formula (A) or formula (B). General formula (A)

[Chemical formula 26]

General formula (B)

[Chemical 27]

These compounds have the general formula (A) or the general formula
After the reducing group represented by RED ₁₁ or RED ₁₂ in (B) is one-electron oxidized, L ₁₁ or L ₁₂ is spontaneously released by a bond cleavage reaction, that is, C (carbon atom)- L ₁₁
Bond or C (carbon atom) -L ₁₂ bond is cleaved,
Along with this, it is a compound that can further emit two or more electrons, preferably three or more electrons.

First, the compound represented by the general formula (A) will be described in detail below. The one-electron-oxidizable reducing group represented by RED ₁₁ in the general formula (A) is R described below.
_A group capable of forming a specific ring by bonding with _111, and specific examples thereof include a divalent group obtained by removing one hydrogen atom at an appropriate position for forming a ring from the following monovalent group. For example, alkylamino group, arylamino group (anilino group, naphthylamino group, etc.), heterocyclic amino group (benzthiazolylamino group, pyrrolylamino group, etc.), alkylthio group, arylthio group (phenylthio group, etc.), heterocyclic thio group Group, alkoxy group, aryloxy group (phenoxy group, etc.), heterocyclic oxy group, aryl group (phenyl group, naphthyl group, anthranyl group, etc.), aromatic or non-aromatic heterocyclic group (here Examples include, for example, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinoxaline ring, tetrahydroquinazoline ring, indoline ring, indole ring, indazole ring, carbazole ring, phenoxazine ring, phenothiazine ring, benzothiazoline ring, pyrrole ring, imidazole ring, Thiazoline ring, piperidi Ring describing the pyrrolidine ring, a morpholine ring, a benzimidazole ring, benzimidazoline ring, benzo-oxazoline ring, a 3,4-methylenedioxyphenyl ring, and the like) (hereinafter, for convenience RED ₁₁ as monovalent Name ). These may have a substituent.

As the substituent, for example, a halogen atom, an alkyl group (including an aralkyl group, a cycloalkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (the position of substitution is not limited) A heterocyclic group containing a quaternized nitrogen atom (for example, a pyridinio group,
Imidazolio group, quinolinio group, isoquinolinio group),
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group,
Oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or Aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group,
Ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group Group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl,
Or (heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide Alternatively, a group containing a phosphoric acid ester structure and the like can be mentioned. These substituents may be further substituted with these substituents.

In the general formula (A), L ₁₁ represents a leaving group which can be eliminated by bond cleavage only after the reducing group represented by RED ₁₁ is one-electron oxidized, and specifically, a carboxy group or a leaving group thereof. Represents a salt or silyl group.

When L ₁₁ represents a salt of a carboxy group, specific counter ions for forming the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ ) and alkaline earth metal ions (Mg ^{2 +} , Ca ²⁺ , Ba ²⁺ ), heavy metal ions (Ag ⁺ , Fe ^{2 + / 3 +} ), ammonium ion, phosphonium ion and the like. When L ₁₁ represents a silyl group, the silyl group specifically represents a trialkylsilyl group, an aryldialkylsilyl group, a triarylsilyl group, and the like, and the alkyl group represents a methyl, ethyl, benzyl, t-butyl group. Examples of the aryl group include a phenyl group.

In the general formula (A), R ₁₁₂ represents a hydrogen atom or a substituent capable of substituting for a carbon atom. When R ₁₁₂ represents a substituent capable of substituting on a carbon atom, examples of the substituent include the same as the examples of the substituent when RED ₁₁ has a substituent. However, R _{11 2} does not represent the same group as L ₁₁ .

In the general formula (A), R ₁₁₁ represents a non-metallic atomic group capable of forming a specific 5-membered or 6-membered cyclic structure together with the carbon atom (C) and RED ₁₁ . The specific 5-membered or 6-membered cyclic structure formed by R ₁₁₁ is a ring corresponding to a tetrahydro body, a hexahydro body or an octahydro body of a 5-membered or 6-membered aromatic ring (including an aromatic heterocycle). Means structure. Here, the hydro form means a ring structure in which a carbon-carbon double bond (or a carbon-nitrogen double bond) existing in an aromatic ring (including an aromatic heterocycle) is partially hydrogenated, The tetrahydro form means a structure in which two carbon-carbon double bonds (or carbon-nitrogen double bonds) are hydrogenated, and the hexahydro form means three carbon-carbon double bonds (or carbon-nitrogen double bonds). (Bond) means a hydrogenated structure, and the octahydro form means four carbon-carbon double bonds.
(Or carbon-nitrogen double bond) means a hydrogenated structure. By being hydrogenated, the aromatic ring becomes a partially hydrogenated non-aromatic ring structure.

Specifically, as an example of a monocyclic 5-membered ring, a pyrrolidine ring, an imidazole corresponding to a tetrahydro body of an aromatic ring such as a pyrrole ring, an imidazole ring, a thiazole ring, a pyrazole ring, an oxazole ring, etc. Examples thereof include a lysine ring, a thiazolidine ring, a pyrazolidine ring and an oxazolidine ring. Examples of the 6-membered monocyclic ring include a tetrahydro body or a hexahydro body of an aromatic ring such as a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.
Examples thereof include a tetrahydropyrimidine ring and a piperazine ring. In the case of a 6-membered condensed ring, for example, a naphthalene ring,
Examples thereof include a tetraline ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, a tetrahydroquinazoline ring, and a tetrahydroquinoxaline ring, which correspond to a tetrahydro body of an aromatic ring such as a quinoline ring, an isoquinoline ring, a quinazoline ring, and a quinoxaline ring. Examples of the tricyclic compound include a tetrahydrocarbazole ring which is a tetrahydro carbazole ring, and an octahydrophenanthridine ring which is an octahydro phenanthridine ring.

These ring structures may be further substituted, and examples of the substituents are the same as those described for the substituents that RED ₁₁ may have. The substituents of these ring structures may be further linked to form a ring, and the ring newly formed here is a non-aromatic carbocycle or heterocycle.

Next, the preferred range of the compound represented by formula (A) of the present invention will be explained. In the general formula (A), L
₁₁ is preferably a carboxy group or a salt thereof. The counter ion of the salt is preferably an alkali metal ion or an ammonium ion, most preferably an alkali metal ion (particularly Li ⁺ , Na ⁺ , K ⁺ ion).

In the general formula (A), RED ₁₁ is preferably an alkylamino group, an arylamino group, a heterocyclic amino group, an aryl group, an aromatic or non-aromatic heterocyclic group. Is a tetrahydroquinolinyl group, a tetrahydroquinoxalinyl group, a tetrahydroquinazolinyl group, an indolyl group, an indolenyl group,
Carbazolyl group, phenoxazinyl group, phenothiazinyl group, benzothiazolinyl group, pyrrolyl group, imidazolyl group, thiazolidinyl group, benzimidazolyl group, benzimidazolinyl group, 3,4-methylenedioxyphenyl-1
-Iyl group is preferred. More preferably arylamino group (especially anilino group), aryl group (especially phenyl group)
Is. When RED ₁₁ represents an aryl group, the aryl group has at least one electron-donating group (the number of electron-donating groups is preferably 4 or less, more preferably 1 to
3) is preferable. Here, the electron-donating group means a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an acylamino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an active methine group, and an electron-rich aromatic heterocyclic group. Group (for example, indolyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, thiazolyl group, benzthiazolyl group, indazolyl group, etc.), a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom (pyrrolidinyl group, indolinyl group, piperidinyl group, Piperazinyl group, morpholino group, etc.). Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, trifluoromethyl group,
It means a cyano group, a nitro group or an imino group. Here, the two electron-withdrawing groups may be bonded to each other to form a cyclic structure. When RED ₁₁ represents an aryl group, the substituent of the aryl group is more preferably an alkylamino group, a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an active methine group, or a non-aromatic nitrogen-containing group substituted with a nitrogen atom. A heterocyclic group, more preferably an alkylamino group, a hydroxy group, an active methine group, a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom, most preferably an alkylamino group, a non-aromatic group substituted with a nitrogen atom. It is a group-containing nitrogen-containing heterocyclic group.

In formula (A), R ₁₁₂ is preferably a hydrogen atom, an alkyl group, an aryl group (such as a phenyl group), an alkoxy group (such as a methoxy group, an ethoxy group, a benzyloxy group), a hydroxy group or an alkylthio group (such as methylthio). Groups, butylthio groups, etc.), amino groups, alkylamino groups, arylamino groups, and heterocyclic amino groups, and more preferably hydrogen atoms, alkyl groups, alkoxy groups, phenyl groups, and alkylamino groups.

In the general formula (A), R ₁₁₁ is preferably
A non-metallic atomic group capable of forming the following specific 5-membered or 6-membered cyclic structure together with a carbon atom (C) and RED ₁₁ . That is, a pyrrole ring which is a monocyclic 5-membered aromatic ring,
Pyrrolidine ring corresponding to tetrahydro form of imidazole ring, imidazolidine ring, etc. A tetrahydro or hexahydro form of a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring, which is a monocyclic 6-membered aromatic ring. For example, piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, piperazine ring and the like. A tetrahydro ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, a tetrahydroquinazoline ring, and a tetrahydro that correspond to a tetrahydro body of a condensed ring 6-membered aromatic ring, which is a naphthalene ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, and a quinoxaline ring. Quinoxaline ring etc. Examples thereof include a tetrahydrocarbazole ring which is a tetrahydro form of a carbazole ring which is a tricyclic aromatic ring, and an octahydrophenanthridine ring which is an octahydro form of a phenanthridine ring. The cyclic structure formed by R ₁₁₁ is more preferably a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a tetrahydropyridine ring, a tetrahydropyrimidine ring, a piperazine ring, a tetrahydroquinoline ring, a tetrahydroquinazoline ring, a tetrahydroquinoxaline ring or a tetrahydrocarbazole ring. , Particularly preferably pyrrolidine ring, piperidine ring, piperazine ring, tetrahydroquinoline ring, tetrahydroquinazoline ring, tetrahydroquinoxaline ring, tetrahydrocarbazole ring, most preferably pyrrolidine ring, piperidine ring and tetrahydroquinoline ring.

Next, the general formula (B) will be described in detail.
RED in the general formula (B)₁₂, L₁₂Is the general formula
RED of (A)₁₁, L₁₁Is a group synonymous with and its preferred
The range is also the same. However, RED₁₂Is the following ring structure
Is a monovalent group except when forming a structure, specifically, RE
D₁₁The groups having the monovalent group name described in 1. can be mentioned. R₁₂₁And
And R₁₂₂Is R in the general formula (A)₁₂₂Is synonymous with
The preferred range is also the same. ED12 has an electron-donating group
Represent R ₁₂₁And RED₁₂, R₁₂₁And R₁₂₂, Or ED₁₂
And RED₁₂And are bonded to each other to form a cyclic structure.
May be.

ED in the general formula (B)₁₂Electron represented by
Donor groups include hydroxy groups, alkoxy groups, mercaps
Group, alkylthio group, arylthio group, heterocyclic thio group
Group, sulfonamide group, acylamino group, alkylamido
Group, arylamino group, heterocyclic amino group, active methyl group
Group, aromatic heterocyclic group with excess electron (for example, indolyl
Group, pyrrolyl group, indazolyl group), nitrogen atom
Non-aromatic nitrogen-containing heterocyclic group (pyrrolidinyl group, piperidine
Dinyl group, indolinyl group, piperazinyl group, morpholin
Group, etc.) and an group substituted with these electron-donating groups.
Reel groups (e.g. p-hydroxyphenyl group, p-dialkyl group)
Ruaminophenyl group, o, p-dialkoxyphenyl group, 4-
A hydroxynaphthyl group). Active methine here
The basis is RED₁₁Is a substituent when represents an aryl group
It is the same as the one explained above. ED ₁₂Preferably as
Hydroxy group, alkoxy group, mercapto group, sulfone
Amido group, alkylamino group, arylamino group, active
Set with methine group, aromatic heterocyclic group with excess electron, nitrogen atom
Non-aromatic nitrogen-containing heterocyclic group to be substituted, and these children
A phenyl group substituted with a pendant group, further comprising a hydroxyl group
Si group, mercapto group, sulfonamide group, alkylamido
Group, arylamino group, active methine group, nitrogen atom
Non-aromatic nitrogen-containing heterocyclic group to be substituted, and these children
A phenyl group substituted with a pendant group (for example, p-hydroxy group)
Phenyl group, p-dialkylaminophenyl group, o, p-dial
(Coxyphenyl group etc.) is preferable.

In the general formula (B), R ₁₂₂ and RED ₁₂ , R
₁₂₂ and R _121, or the ED ₁₂ and RED _{1 2,,} they may form a ring structure bonded to each other. The cyclic structure formed here is a non-aromatic carbon ring or hetero ring, a 5-membered to 7-membered monocyclic or condensed ring, and a substituted or unsubstituted cyclic structure. When R ₁₂₂ and RED ₁₂ form a ring structure, specific examples thereof include a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, an imidazoline ring,
Thiazolidine ring, thiazoline ring, pyrazolidine ring, pyrazoline ring, oxazolidine ring, oxazoline ring, indane ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, indoline ring, tetralin ring, tetrahydroquinoline ring,
Tetrahydroisoquinoline ring, tetrahydroquinoxaline ring, tetrahydro-1,4-oxazine ring, 2,3-dihydrobenzo-1,4-oxazine ring, tetrahydro-1,4-thiazine ring, 2,3-dihydrobenzo-1,4 -Thiazine ring, 2,3-dihydrobenzofuran ring, 2,3-dihydrobenzothiophene ring and the like can be mentioned. When ED ₁₂ and RED ₁₂ form a ring structure, ED ₁₂ preferably represents an amino group, an alkylamino group or an arylamino group, and specific examples of the ring structure formed include a tetrahydropyrazine ring, a piperazine ring,
Examples thereof include a tetrahydroquinoxaline ring and a tetrahydroisoquinoline ring. When R ₁₂₂ and R ₁₂₁ form a ring structure, specific examples thereof include a cyclohexane ring and a cyclopentane ring.

More preferred compounds among the compounds represented by the general formula (A) of the present invention are the following general formulas (10) to (12).
Further, more preferred compounds represented by the general formula (B) are represented by the following general formulas (13) and (14).

[0062]

[Chemical 28]

In the general formulas (10) to (14), L ₁₀₀ ,
L ₁₀₁ , L ₁₀₂ , L ₁₀₃ and L ₁₀₄ have the same meaning as L ₁₁ in formula (A), and their preferable ranges are also the same. R
₁₁₀₀ and R ₁₁₀₁ , R ₁₁₁₀ and R ₁₁₁₁ , R ₁₁₂₀ , and R ₁₁₂₁ and R
₁₁₃₀ and R ₁₁₃₁ , and R ₁₁₄₀ and R ₁₁₄₁ are each represented by the general formula (B)
R ₁₂₁ and R ₁₂₂ have the same meanings, and their preferable ranges are also the same. ED ₁₃ and ED ₁₄ are each represented by the general formula (B).
Of ED ₁₂ having the same meaning, and the preferred range is also the same. X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , and X ₁₄ each represent a substituent capable of substituting on the benzene ring, and m ₁₀ , m ₁₁ , m ₁₂ , and
m ₁₃ and m ₁₄ each represent an integer of 0 to 3, and when these are plural, plural X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may be the same or different. Y ₁₂ and Y ₁₄ are an amino group, an alkylamino group, an arylamino group, a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom (pyrrolyl group, piperidinyl group, indolinyl group, piperazino group, morpholino group, etc.), hydroxy Represents a group and an alkoxy group.

Z ₁₀ , Z ₁₁ and Z ₁₂ represent a non-metal atomic group capable of forming a specific ring structure. The specific ring structure formed by Z ₁₀ is a 5-membered or 6-membered, monocyclic or condensed ring, tetracyclic structure or hexahydro structure of a nitrogen-containing aromatic heterocycle, specifically, a pyrrolidine ring, Imidazolidine ring, thiazolidine ring, pyrazolidine ring, piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, piperazine ring, tetrahydroquinoline ring,
Examples include a tetrahydroisoquinoline ring, a tetrahydroquinazoline ring, a tetrahydroquinoxaline ring, and the like. The specific ring structure formed by Z ₁₁ is a tetrahydroquinoline ring or a tetrahydroquinoxaline ring. Z
_The specific ring structure formed by ₁₂ is a tetralin ring, a tetrahydroquinoline ring, or a tetrahydroisoquinoline ring.

R _N11 and R _N13 are each a hydrogen atom or a substituent capable of substituting for a nitrogen atom. Specific examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and an acyl group, and an alkyl group and an aryl group are preferable.

The substituent capable of substituting on the benzene ring represented by X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ is a substituent which may be possessed by RED ₁₁ of the general formula (A). Specific examples are the same as the examples. Preferably, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, an alkoxy group (a group containing a repeating ethyleneoxy group or a propyleneoxy group unit (Including), (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group,
Examples thereof include thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, nitro group, (alkyl, aryl or heterocycle) thio group, (alkyl or aryl) sulfonyl group and sulfamoyl group. m ₁₀ , m ₁₁ , m ₁₂ , m ₁₃ , and m ₁₄ are preferably 0 to 2, and more preferably 0 or 1.

Y ₁₂ and Y ₁₄ are preferably an alkylamino group, an arylamino group, a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom, a hydroxy group or an alkoxy group, more preferably an alkylamino group or a nitrogen atom. A 5- or 6-membered non-aromatic nitrogen-containing heterocyclic group substituted with an atom or a hydroxy group, most preferably an alkylamino group (particularly a dialkylamino group) or a 5- or 6-membered non-aromatic containing nitrogen-substituted heteroaromatic group. It is a nitrogen heterocyclic group.

In the general formula (13), R₁₁₃₁And X₁₃, R
₁₁₃₁And R_N13, R₁₁₃₀And X₁₃, Or R₁₁₃₀And R_N13And
They may be bonded to each other to form a ring structure. Also the general formula
R in (14)₁₁₄₁And X₁₄, R₁₁₄₁And R₁₁₄₀, ED₁₄
And X₁₄, Or R₁₁₄₀And X₁₄And combine to form a cyclic structure
It may be formed. The annular structure formed here is
Non-aromatic carbocyclic or heterocyclic ring having 5 to 7 members
Substituted or unsubstituted ring, which is a membered monocyclic or condensed ring
It is a structure. R in the general formula (13)₁₁₃₁And X ₁₃Conclude
When combined to form a ring structure, and R₁₁₃₁And R_N13
When and combine to form a ring structure, form a ring structure
As in the case of not using the compound represented by the general formula (13),
This is a preferred example. R in the general formula (13)₁₁₃₁And X₁₃
Specific examples of the ring structure formed by
(In this case, R₁₁₃₁Represents a single bond), tetra
Hydroquinoline ring, tetrahydroquinoxaline ring, 2,3-
Dihydrobenzo-1,4-oxazine ring, 2,3-dihydroben
Zo-1,4-thiazine ring, and the like. Particularly preferred
Is indoline ring, tetrahydroquinoline ring, tetrahydr
It is a loquinoxaline ring. R in the general formula (13)₁₁₃₁
And R_N13Specific examples of the ring structure formed by
Lysine ring, Pyrroline ring, Imidazolidine ring, Imidazori
Ring, thiazolidine ring, thiazoline ring, pyrazolidine
Ring, pyrazoline ring, oxazolidine ring, oxazoline
Ring, piperidine ring, piperazine ring, morpholine ring, tet
Lahydropyridine ring, tetrahydropyrimidine ring, in
Drin ring, tetrahydroquinoline ring, tetrahydroiso
Quinoline ring, tetrahydroquinoxaline ring, tetrahydr
B-1,4-oxazine ring, 2,3-dihydrobenzo-1,4-oxa
Gin ring, tetrahydro-1,4-thiazine ring, 2,3-dihydro
Benzo-1,4-thiazine ring, 2,3-dihydrobenzofuran
Ring, 2,3-dihydrobenzothiophene ring, etc.
It Particularly preferred is a pyrrolidine ring, piperidine ring, or tet
A lahydroquinoline ring and a tetrahydroquinoxaline ring
It

In the general formula (14), when R ₁₁₄₁ and X ₁₄ are combined to form a cyclic structure and when ED ₁₄ and X ₁₄ are combined to form a cyclic structure, no ring structure is formed. As in the case, it is a preferable example of the compound represented by the general formula (14). _{Examples of} the cyclic structure formed by combining R ₁₁₄₁ and X ₁₄ in the general formula (14) include an indane ring, a tetralin ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, and an indoline ring. ED ₁₄
Examples of the cyclic structure formed by the combination of X and X ₁₄ include a tetrahydroisoquinoline ring and a tetrahydrocinnoline ring.

Next, the compound of type 2 will be described.
The compound of type 2 is a compound which, after being one-electron-oxidized into a one-electron oxidant, releases another one electron with the carbon-carbon bond cleavage reaction for the first time. . Here, the bond cleavage reaction means the cleavage of carbon-carbon bond, and the cleavage of carbon-hydrogen bond may be accompanied.

Among the compounds of type 2, preferred compounds are represented by general formula (C).

General formula (C)

[Chemical 29]

After the reducing group represented by RED ₂ is one-electron oxidized, L ₂ is spontaneously released by a bond cleavage reaction, that is, the C (carbon atom) -L ₂ bond is cleaved. As a result, it is a compound that can further emit one electron.

However, the compound of type 2 is a compound having two or more (preferably 2 to 6, more preferably 2 to 4) groups capable of adsorbing to silver halide in the molecule. More preferably, it is a compound having a nitrogen-containing heterocyclic group substituted with two or more mercapto groups as an adsorptive group. The adsorptive group will be described later.

In the general formula (C), RED ₂ is the general formula (B).
Of RED ₁₂ and has the same preferable range. L ₂ represents a carboxy group or a salt thereof, and the counter ion forming the salt is represented by L _{11 of the} general formula (A).
Is the same as that described above, and its preferable range is also the same. R ₂₁ and R ₂₂ each represent a hydrogen atom or a substituent, which have the same meaning as R _{112 in} formula (A), and the preferred ranges are also the same. RED ₂ and R ₂₁ may combine with each other to form a ring structure.

The ring structure formed here is a non-aromatic 5- to 7-membered carbon ring or hetero ring, which may be a single ring or a condensed ring and has a substituent. Good. Specific examples of the ring structure include, for example, indoline ring, 2,3-dihydrobenzothiophene ring, 2,3-dihydrobenzofuran ring, 1,2-dihydropyridine ring, 1,4-dihydropyridine ring, benzo-α-pyran ring, Benzothiazoline ring, benzoxazoline ring, benzimidazoline ring,
Examples thereof include a 1,2-dihydroquinoline ring, a 1,2-dihydroquinazoline ring, a 1,2-dihydroquinoxaline ring, a chroman ring, and an isochroman ring. Preferably, an indoline ring, a 2,3-dihydrobenzothiophene ring,
1,2-dihydropyridine ring, benzothiazoline ring, benzoxazoline ring, benzimidazoline ring, 1,2-
Dihydroquinoline ring, 1,2-dihydroquinazoline ring,
1,2-dihydroquinoxaline ring etc. are mentioned, an indoline ring, a benzothiazoline ring, a benzimidazoline ring and a 1,2-dihydroquinoline ring are more preferable, and an indoline ring is particularly preferable.

Next, the compound of type 3 will be described.
The compound of type 3 is a compound characterized in that a one-electron oxidation product produced by one-electron oxidation can release one or more electrons after undergoing a subsequent bond formation process. The formation process is carbon-carbon,
It means the formation of interatomic bonds such as carbon-nitrogen, carbon-sulfur, carbon-oxygen.

The compound of type 3 is preferably obtained by reacting a one-electron oxidation product produced by one-electron oxidation with a carbon-carbon double bond site or a carbon-carbon triple bond site coexisting in the molecule. It is a compound characterized by being capable of further releasing one or more electrons after forming a bond.

The one-electron oxidant produced by one-electron oxidation of the type 3 compound is a cation radical species, but it may be a neutral radical species accompanied by elimination of a proton therefrom. This one-electron oxidant (cation radical species or radical species) is present at the carbon-carbon double bond site or carbon-carbon triple bond site existing in the same molecule,
Generally, a chemical reaction of a type called “addition cyclization reaction” is caused to form an interatomic bond such as carbon-carbon, carbon-nitrogen, carbon-sulfur, and carbon-oxygen to form a new ring structure in the molecule. Form. At the same time or after that, 1 more
Type 3 at the point where electrons or more are emitted
There is a characteristic of the compound.

More specifically, the type 3 compound produces a radical species having a new ring structure by this cycloaddition reaction after being subjected to one-electron oxidation. Along with this, the second electron is further emitted and has a characteristic of being oxidized.

Compounds of type 3 are further provided that the two-electron oxidant so formed is then, in some cases, after undergoing a hydrolysis reaction, and in other cases, directly, also with the proton transfer. Initiate a mutagenic reaction, and then 1
Those having the ability to emit electrons or more, usually two or more electrons and be oxidized are included. Alternatively, those having the ability to directly oxidize one or more electrons, usually two or more electrons, directly from the two-electron oxidation product without going through such tautomerization reaction are included. .

Compounds of type 3 preferably have the general formula
It is represented by (D). General formula (D)

[Chemical 30]

RED in the general formula (3)₃Is the general formula
(B) RED₁₂Represents a group synonymous with. RED₃As preferred
Specifically, an arylamino group, a heterocyclic amino group, or
Hydroxy group, mercapto group, alkylthio group, methyl
Substituted with a group selected from the group consisting of
Aryl group or heterocyclic group. RED ₃But
When representing an arylamino group, for example, an anilino group, naphth
A tylamino group and the like can be mentioned. Heterocyclic amino group
A telocycle is an aromatic or non-aromatic, monocyclic or fused ring.
A heterocyclic ring of at least one aromatic ring
Preferably, it is included as a structure. Where the aromatic ring is
Included as a split structure is that 1) the heterocycle itself is an aromatic ring.
Yes, 2) an aromatic ring is condensed to a hetero ring, 3)
Whether the aromatic ring is substituted for the terror ring,
Good, but 1) or 2) is preferable. Where the amino group is
Directly on an aromatic ring included as a partial structure in the heterocycle
Has been replaced. Examples of the heterocycle include pyrrole
Ring, indole ring, indoline ring, imidazole ring,
Nzoimidazole ring, benzimidazoline ring, thiazo
Ring, benzothiazole ring, benzothiazoline ring, oki
Sazole ring, benzoxazole ring, benzoxazoli
Ring, quinoline ring, tetrahydroquinoline ring, quinoxa
Phosphorus ring, tetrahydroquinoxaline ring, quinazoline ring,
Tetrahydroquinazoline ring, pyridine ring, isoquinoline
Ring, thiophene ring, benzothiophene ring, 2,3-dihi
Drobenzothiophene ring, furan ring, benzofuran ring,
2,3-dihydrobenzofuran ring, carbazole ring, fluorine
Enothiazine ring, phenoxazine ring, phenazine ring, etc.
Can be mentioned. RED₃Is an arylamino group or hetero
When representing a ring amino group, the
Group, and the amino group of the heterocyclic amino group are further defined.
It may be substituted with any substituent, and
To further form a ring structure with the aryl group or the heterocyclic group.
It may be formed. An example of this is, for example,
Indrin ring, tetrahydroquinoline ring, carbazole ring
And so on.

RED ₃ is a hydroxy group, a mercapto group,
When representing an aryl group or a heterocyclic group substituted with a methyl group, an alkylthio group, an amino group, or the like, examples of the aryl group include a phenyl group and a naphthyl group,
Examples of the hetero ring of the hetero ring group include the same as those described for the “hetero ring of the hetero ring amino group”. Further, here, the methyl group may have an arbitrary substituent, and the substituent may form a ring structure with the aryl group or the heterocyclic group. Examples of such a ring structure include a tetralin ring and an indane ring. On the other hand, the amino group may have an alkyl group, an aryl group or a heterocyclic group as a substituent, and these substituents may form a ring structure with the aryl group or the heterocyclic group. Examples of such a ring structure include a tetrahydroquinoline ring, an indoline ring, a carbazole ring and the like. RED ₃ is preferably an arylamino group, or an aryl group or a heterocyclic group substituted with a hydroxy group, a mercapto group, a methyl group or an amino group, more preferably an arylamino group, a mercapto group, a methyl group or an amino group. It is an aryl group or a heterocyclic group substituted with a group. RED ₃ is particularly preferably an arylamino group, or an aryl group or heterocyclic group substituted with a methyl group or an amino group. The arylamino group is preferably an anilino group or a naphthylamino group, and particularly preferably an anilino group. The substituent of the anilino group includes a chloro atom, an alkyl group, an alkoxy group, an acylamino group, a sulfamoyl group, a carbamoyl group, a ureido group, a sulfonamide group, an alkoxycarbonyl group, a cyano group, an alkyl or arylsulfonyl group, and a heterocyclic group. Are preferred. The aryl group or heterocyclic group substituted with a hydroxy group is preferably, for example, hydroxyphenyl group, 5-hydroxyindoline ring group, 6-hydroxy-1,2,3,4-
Examples thereof include a tetrahydroquinoline ring group, and among them, a hydroxyphenyl group is particularly preferable. The aryl group or heterocyclic group substituted with a mercapto group is preferably, for example, a mercaptophenyl group, a 5-mercaptoindoline ring group, a 6-mercapto-1,2,3,4-tetrahydroquinoline ring group, and the like, Among them, a mercaptophenyl group is particularly preferable. The aryl group or heterocyclic group substituted with a methyl group is preferably, for example, methylphenyl group, ethylphenyl group, isopropylphenyl group, 3-methylindole ring group, 3-isopropylindole ring group, 5-methylindole ring group, 5-methylindoline ring group, 6-methyl-1,2,3,4-tetrahydroquinoline ring group, 6-methyl-1,2,3,4
-Tetrahydroquinoxaline ring group etc. are mentioned.

The aryl group or heterocyclic group substituted with an amino group is preferably, for example, methylaminophenyl group, octylaminophenyl group, dodecylaminophenyl group, dimethylaminophenyl group, benzylaminophenyl group, phenylaminophenyl group. , Methylaminonaphthyl group, 5-methylaminotetralin, 1-butylamino-3,4-methylenedioxyphenyl group, 3-
Examples thereof include a methylaminopyrrole ring group, a 3-ethylaminoindole ring group, a 5-benzylaminoindoline ring group, a 2-aminoimidazole ring group, a 2-methylaminothiazole ring group, and a 6-phenylaminobenzothiazole ring group. Of these, a phenyl group substituted with an alkylamino group or a phenylamino group is more preferable, and a phenyl group substituted with an alkylamino group is particularly preferable. Examples of the substituent of the aryl group or heterocyclic group substituted with a hydroxy group, a mercapto group, a methyl group or an amino group include a chloro atom, an alkyl group, an alkoxy group, an acylamino group, a sulfamoyl group, a carbamoyl group, a ureido group and a sulfone. Amide group,
An alkoxycarbonyl group, a cyano group, an alkyl or arylsulfonyl group, a heterocyclic group, an alkylamino group, an arylamino group and the like are preferable.

In formula (D), the reactive group represented by Y ₃ specifically means an organic group containing at least one carbon-carbon double bond site or carbon-carbon triple bond site. The carbon-carbon double bond or the carbon-carbon triple bond may have a substituent, and the substituent has a general formula
The same as those described as the substituent that RED _{11 of} (A) may have may be mentioned. Of these, an alkyl group, an aryl group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, an electron donating group and the like are preferable.
Here, the electron donating group is an alkoxy group, a hydroxy group, an amino group, an alkylamino group, an arylamino group,
Heterocyclic amino groups, sulfonamide groups, acylamino groups, active methine groups, mercapto groups, alkylthio groups, arylthio groups, and aryl groups having these groups as substituents. Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, It means an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group or an imino group. Here, the two electron-withdrawing groups may be bonded to each other to form a cyclic structure.

When Y ₃ represents a carbon-carbon double bond site, its substituent is more preferably an alkyl group, an alkoxycarbonyl group, a carbamoyl group, an electron donating group, etc., and an electron donating group is preferred here. Is an alkoxy group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a sulfonamide group, an acylamino group, an active methine group, a mercapto group, an alkylthio group, and a phenyl group having an electron-donating group as a substituent. It is a base. It is also preferable that an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group or the like as a substituent is bonded to each other to form a ring structure containing a carbon-carbon double bond, and specifically, for example, 2,3-dihydro. -Γ
—Pyran ring group, cyclohexene ring group, 1-thia-2-cyclohexen-3-yl group, tetrahydropyridine ring group and the like.

When Y ₃ represents an organic group containing a carbon-carbon double bond site, the substituents may be bonded to each other to form a cyclic structure. The cyclic structure formed here is a non-aromatic, 5- to 7-membered carbon ring or hetero ring.
When Y ₃ represents a carbon-carbon triple bond site, its substituent is preferably a hydrogen atom, an alkoxycarbonyl group, a carbamoyl group, an electron donating group, etc., and the electron donating group is preferably an alkoxy group or an amino group. A group, an alkylamino group, an arylamino group, a heterocyclic amino group, a sulfonamide group, an acylamino group, an active methine group, a mercapto group, an alkylthio group, and a phenyl group having these electron-donating groups as substituents.

In the general formula (D), the reactive group represented by Y ₃ is more preferably an organic group containing a carbon-carbon double bond. In the general formula (D), L ₃ is RED ₃ and Y ₃
Represents a linking group for linking with, specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, -O-, -S-,
-NR _N- , -C (= O)-, -SO _2- , -SO-,-
P (= O)-represents a single group or a combination of these groups. Here, R _N represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The linking group represented by L ₃ may have a substituent. As a substituent,
RED ₁₁ of the general formula (A) may be the same as those described as the substituent which may have.

The group represented by L ₃ in the general formula (D) is a group represented by the general formula
A cationic radical species produced by oxidation of RED _{3 of} (D) or a radical species produced by elimination of a proton therefrom reacts with a reactive group represented by Y ₃ of the general formula (3). when a bond is formed, groups associated with this, L ₃
It is preferable that it can form a 3- to 7-membered cyclic structure.

Preferred examples of L ₃ include a single bond, an alkylene group, an arylene group (particularly a phenylene group), and -C (=
O)-group, -O- group, -NH- group, -N (alkyl group)-
Examples thereof include a group and a divalent linking group composed of a combination of these groups.

Among the compounds represented by the general formula (D), preferable compounds are represented by the following general formulas (D-1) to (D-4).

[0093]

[Chemical 31]

In the general formulas (D-1) to (D-4),
A₁₀₀, A₂₀₀, A₃₀₀, A₄₀₀Is an aryl group or hetero
Represents a ring group, and its preferred range is RED of the general formula (D).₃
Is the same as the preferred range of. L₃₀₁, L₃₀₂, L₃₀₃,
L₃₀₄Represents a linking group, which is L in the general formula (D).₃Synonymous with
It represents a group, and its preferable range is also the same.
Y₁₀₀, Y_{20 0}, Y₃₀₀, Y₄₀₀Represents a reactive group, which is
Y in general formula (D)₃And a preferred range thereof
Is also the same. R₃₁₀₀, R₃₁₁₀, R₃₂₀₀, R₃₂₁₀，
R₃₃₁₀Represents a hydrogen atom or a substituent. R₃₁₀₀, R₃₁₁₀
Is preferably a hydrogen atom, an alkyl group or an aryl group
is there. R₃₂₀₀, R₃₃₁₀Is preferably a hydrogen atom. R
₃₂₁₀Is preferably a substituent, and the substituent is preferably
Is an alkyl group or an aryl group. R₃₁₁₀Is A₁₀₀
And R₃₂₁₀Is A₂₀₀And R₃₃₁₀Is A₃₀₀And each combined
And may form a ring structure. Ring formed here
The structure is preferably a tetralin ring, an indane ring, or a tetra ring.
Examples include trahydroquinoline ring and indoline ring. X
₄₀₀Is a hydroxy group, mercapto group, alkylthio group
, Preferably a hydroxy group or a mercapto group,
Preferred is a mercapto group.

Here, the general formulas (D-1) to (D-4) and the general formulas
Explaining the relationship with (D), A in the general formula (D-1)₁₀₀Is
Methyl group: -CH (R₃₁₁₀) (R₃₁₀₀) Replaced by Ally
A group of general formula (D-2)₂₀₀
Is an amino group: -N (R₃₂₁₀) (R ₃₂₀₀) Replaced by Ally
Represents a group or a heterocyclic group, A of the general formula (D-4)_Four
00Is X₄₀₀The hydroxy group, mercapto group, or
Or an aryl group substituted with an alkylthio group or
It represents a telocyclic group and is represented by A in the general formula (D-3).₃₀₀-N (R ₃₃₁₀)
Similarly, a group represented by-is an arylamino group or hetero.
Represents a ring amino group.

Among the general formulas (D-1) to (D-4), more preferable compounds are the general formulas (D-1), (D-2) and (D-4).
Is a compound represented by.

Next, the compound of type 4 will be described.
The compound of type 4 is a compound having a ring structure in which a reducing group is substituted, and after the reducing group is oxidized by one electron, the ring structure is cleaved to release one or more electrons. Compound. Type 4 compound is 1
The ring structure is cleaved after undergoing electron oxidation. The ring-cleavage reaction as used herein refers to one of the types shown below.

[0098]

[Chemical 32]

In the formula, the compound a represents a type 4 compound. In the compound a, D represents a reducing group, and X and Y represent atoms in the ring structure forming a bond that cleaves after one-electron oxidation. First, compound a is one-electron oxidized to give one-electron oxidant b
To generate. From here, the single bond of DX becomes a double bond, and at the same time, the bond of XY is cleaved to form ring-opened product c.
Alternatively, the radical intermediate d is generated from the one-electron oxidant b with the elimination of a proton, and the ring-opened compound e is similarly generated from this.
In some cases, the route for generating is taken. The compound of the present invention is characterized in that one or more electrons are subsequently released from the ring-opened body c or e thus produced.

The ring structure of the type 4 compound is 3
Is a 7-membered carbocyclic or heterocyclic ring, and represents a monocyclic or condensed, saturated or unsaturated, non-aromatic ring. It is preferably a saturated ring structure, and more preferably a 3-membered ring or 4-membered ring. Preferred ring structures include cyclopropane ring, cyclobutane ring, oxirane ring, oxetane ring, aziridine ring, azetidine ring, episulfide ring,
Examples include a thietane ring. More preferably a cyclopropane ring, a cyclobutane ring, an oxirane ring, an oxetane ring,
An azetidine ring is preferable, and a cyclopropane ring, a cyclobutane ring, and an azetidine ring are particularly preferable. The ring structure may have a substituent.

Compounds of type 4 preferably have the general formula (E)
Or represented by (F). General formula (E)

[Chemical 33]

General formula (F)

[Chemical 34]

In the general formulas (E) and (F), RE
D₄₁And RED₄₂Are RED of the general formula (B), respectively.₁₂
And the preferred range is also the same.
It R ₄₀~ R₄₄And R₄₅~ R₄₉Are hydrogen atoms
Alternatively, it represents a substituent. RED as a substituent₁₂Has
The same thing as the substituent which may be mentioned is mentioned. General formula (F)
At Z₄₂Is -CR₄₂₀R₄₂₁-, -NR₄₂₃-,
Or represents -O-. R here₄₂₀, R₄₂₁Each is water
Represents an elementary atom or a substituent, R₄₂₃Is a hydrogen atom, Archi
Represents a group, an aryl group or a heterocyclic group.

In the general formula (E), R ₄₀ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an alkylamino group, an arylamino group or a heterocyclic group. Amino group,
Alkoxycarbonyl group, acyl group, carbamoyl group,
Represents a cyano group, a sulfamoyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, particularly preferably a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an alkoxycarbonyl group, and a carbamoyl group.

R _{41 to} R ₄₄ are at least one of these.
Is a donor group, R ₄₁ and R ₄₂ , or R
_It is preferred that both ₄₃ and R ₄₄ are electron withdrawing groups.
More preferably, at least one of R _{41 to} R ₄₄ is a donor group. More preferably, at least one of R _{41 to} R ₄₄ is a donor group, and the group which is not a donor group in R _{41 to} R ₄₄ is a hydrogen atom or an alkyl group.

The donor group referred to here is a hydroxy group, an alkoxy group, an aryloxy group, a mercapto group,
Acylamino group, sulfonylamino group, active methine group,
Alternatively, it is a group selected from the group of preferable groups as RED ₄₁ and RED ₄₂ . The donor group is preferably an alkylamino group, an arylamino group, a heterocyclic amino group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (which may be a single ring or a condensed ring), and a nitrogen atom. Substituted non-aromatic nitrogen-containing heterocyclic group, a phenyl group substituted with at least one electron-donating group (here, the electron-donating group is a hydroxy group, an alkoxy group, an aryloxy group, an amino group,
An alkylamino group, an arylamino group, a heterocyclic amino group, or a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom) is used. More preferably an alkylamino group, an arylamino group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (here, the aromatic heterocycle represents an indole ring, a pyrrole ring, a carbazole ring), an electron A phenyl group substituted with a donor group (in particular, a phenyl group substituted with three or more alkoxy groups, a hydroxy group or a phenyl group substituted with an alkylamino group or an arylamino group) is used. Particularly preferably, an arylamino group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (here, it represents a 3-indolyl group), a phenyl group substituted with an electron-donating group (here, particularly (A phenyl group substituted with a trialkoxyphenyl group, an alkylamino group or an arylamino group) is used. The electron-withdrawing group is the same as already described in the description of the active methine group.

The preferred range of R ₄₅ in the general formula (F) is the same as that of R _{40 in} the general formula (E). R ₄₆
~ R ₄₉ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a mercapto group, It is an arylthio group, an alkylthio group, an acylamino group or a sulfoneamino group, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Particularly preferred R _{46 to} R ₄₉ are those in which Z ₄₂ is -C.
R ₄₂₀ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylamino group or an arylamino group in the case of a group represented by R ₄₂₁ −, and hydrogen when Z ₄₂ represents —NR ₄₂₃ —. An atom, an alkyl group, an aryl group, or a heterocyclic group, and when Z ₄₂ represents —O—, it is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Z ₄₂ is preferably —CR ₄₂₀ R ₄₂₁ — or —NR ₄₂₃ —, and more preferably —NR ₄₂₃ —. R ₄₂₀ and R ₄₂₁ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an amino group, a mercapto group, an acylamino group or a sulfoneamino group, and Preferred are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group and an amino group. R ₄₂₃ preferably represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a t-amyl group, a benzyl group or a diphenylmethyl group. , Allyl group, phenyl group, naphthyl group, 2-pyridyl group, 4-pyridyl group, and 2-thiazolyl group.

When each group of R _{40 to} R ₄₉ and R ₄₂₀ , R ₄₂₁ and R ₄₂₃ is a substituent, it preferably has a total carbon number of 40 or less, more preferably a total carbon number of 30 or less, Particularly preferably, the total carbon number is 15 or less. Further, these substituents may be bonded to each other or to other sites in the molecule (RED ₄₁ , RED ₄₂ or Z ₄₂ ) to form a ring.

The compounds of types 1, 3, and 4 of the present invention are
"Compounds having an adsorptive group for silver halide in the molecule"
Or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. The type 2 compound is a “compound having two or more groups capable of adsorbing silver halide in the molecule”.

In the compounds of types 1 to 4 of the invention, the adsorptive group to silver halide is a group which directly adsorbs to silver halide or a group which promotes adsorption to silver halide. Is a mercapto group (or salt thereof), a thione group (-C (= S)-), a heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom, a sulfide group, a cation. And a ethynyl group. However, the type 2 compound of the present invention does not include a sulfide group as an adsorptive group.

The mercapto group (or its salt) as the adsorptive group means the mercapto group (or its salt) itself, and more preferably, a heterocyclic group substituted with at least one mercapto group (or its salt). Alternatively, it represents an aryl group or an alkyl group. Here, the heterocyclic group is a 5-membered to 7-membered, monocyclic or condensed ring, aromatic or non-aromatic heterocyclic group, for example, an imidazole ring group,
Thiazole ring group, oxazole ring group, benzimidazole ring group, benzthiazole ring group, benzoxazole ring group, triazole ring group, thiadiazole ring group, oxadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, quinoline Examples thereof include a ring group, an isoquinoline ring group, a pyrimidine ring group and a triazine ring group. Further, it may be a heterocyclic group containing a quaternized nitrogen atom, and in this case, the substituted mercapto group may be dissociated to form a meso ion. Examples of such a heterocyclic group include imidazolium ring group, Pyrazolium ring group, thiazolium ring group, triazolium ring group, tetrazolium ring group, thiadiazolium ring group, pyridinium ring group, pyrimidinium ring group, triazinium ring group, and the like, among which triazolium ring group
(For example, 1,2,4-triazolium-3-thiolate ring group) is preferable. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. When the mercapto group forms a salt, as a counter ion, a cation such as an alkali metal, an alkaline earth metal, or a heavy metal (Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ag ⁺ , Zn) is used.
²⁺ ), ammonium ion, quaternized nitrogen atom-containing heterocyclic group, phosphonium ion and the like.

The mercapto group as the adsorptive group may be tautomerized into a thione group, specifically, a thioamide group (here, -C (= S) -NH- group),
And a group containing a partial structure of the thioamide group, that is,
A chain or cyclic thioamide group, a thioureido group, a thiourethane group, a dithiocarbamic acid ester group and the like can be mentioned. Here, examples of the ring include a thiazolidine-2-thione group, an oxazolidine-2-thione group, 2-
Examples thereof include a thiohydantoin group, a rhodanine group, an isorhodanine group, a thiobarbituric acid group, and a 2-thioxo-oxazolidin-4-one group.

The thione group as an adsorptive group means that the mercapto group cannot be tautomerized (including the case where the mercapto group becomes a thione group by tautomerization).
(Having no hydrogen atom at the position), a chain or cyclic thioamide group, a thioureido group, a thiourethane group, or a dithiocarbamic acid ester group is also included.

The heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom as an adsorptive group means a -NH- group capable of forming iminosilver (> NAg). -Containing heterocyclic group having a partial structure of, or "-S-" group, "-Se-" group, or "-Te" capable of coordinating to silver ion by a coordination bond
A heterocyclic group having a "" group or a "= N-" group as a partial structure of the heterocycle, examples of the former include a benzotriazole group, a triazole group, an indazole group, a pyrazole group, a tetrazole group, a benzimidazole group, and an imidazole group. Examples of the latter include thiophene group, thiazole group, oxazole group, benzothiazole group, benzoxazole group, thiadiazole group, oxadiazole group, triazine group, selenazole group, benzselenoazole group, tellurazole group. Group, a benztelluazole group, etc. The former is preferable.

A sulfide group as an adsorptive group means "-S
All groups having a partial structure of "" are mentioned, but preferably alkyl (or alkylene) -S-alkyl (or alkylene), aryl (or arylene) -S-
A group having a partial structure of alkyl (or alkylene), aryl (or arylene) -S-aryl (or arylene). Furthermore, these sulfide groups may form a cyclic structure or may be a -SS- group. Specific examples of the case of forming a cyclic structure include a thiolane ring, a 1,3-dithiolane ring or a 1,2-dithiolane ring, a thian ring, a dithian ring, tetrahydro-1,
Examples include groups containing a 4-thiazine ring and the like. Particularly preferred as a sulfide group is alkyl (or alkylene)-
A group having a partial structure of S-alkyl (or alkylene).

The cationic group as the adsorptive group means a group containing a quaternized nitrogen atom, and specifically includes an ammonio group or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom. It is a base. Here, the ammonio group is a trialkylammonio group, a dialkylarylammonio group,
Alkyldiarylammonio groups and the like, for example, benzyldimethylammonio group, trihexylammonio group,
Examples thereof include a phenyldiethylammonio group. Examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinio group, a quinolinio group, an isoquinolinio group, and an imidazolio group. A pyridinio group and an imidazolio group are preferable, and a pyridinio group is particularly preferable. The nitrogen-containing heterocyclic group containing a quaternized nitrogen atom may have any substituent, but in the case of a pyridinio group and an imidazolio group, the substituent is preferably an alkyl group, an aryl group or an acylamino group. , A chloro atom, an alkoxycarbonyl group, a carbamoyl group, and the like. In the case of a pyridinio group, a phenyl group is particularly preferable as the substituent.

An ethynyl group as an adsorptive group means -C≡C
It means an H group, and the hydrogen atom may be substituted. The adsorptive group may have any substituent. Incidentally, specific examples of the adsorptive group are further described in JP-A No. 11-9535.
No. 5, the description of which is described in pages 4-7 is mentioned.

Preferred as the adsorptive group are mercapto-substituted nitrogen-containing heterocyclic groups (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1 group). , 3,4-oxadiazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.), dimercapto-substituted heterocyclic group (eg 2,4-di Mercaptopyrimidine group, 2,4-dimercaptotriazine group, 3,5-dimercapto-1,2,4-triazole group, 2,5-dimercapto-1,3-thiazole group, etc.), or imino silver (> NAg) A nitrogen-containing heterocyclic group having a —NH— group capable of forming as a heterocyclic partial structure (for example, a benzotriazole group, a benzene Imidazole group, an indazole group). The adsorptive group may be substituted anywhere in the general formulas (A) to (F), but the general formulas (A) to (D).
, RED ₁₁ , RED ₁₂ , RED ₂ , RED
₃ , in the general formulas (E) and (F), RED ₄₁ , R
₄₁ , RED ₄₂ , and R _{46 to} R ₄₈ are preferred, and further, all of the general formulas (A) to (F) and RED ₁₁ to
More preferably, it is substituted with RED ₄₂ .

The partial structure of the spectral sensitizing dye is a group containing a chromophore of the spectral sensitizing dye, which is a residue obtained by removing an arbitrary hydrogen atom or a substituent from the spectral sensitizing dye compound. The partial structure of the spectral sensitizing dye may be substituted in any of the general formulas (A) to (F), but in the general formulas (A) to (D), RED ₁₁ , RED ₁₂ , RED ₂ and RED are used. ₃ , in the general formulas (E) and (F), RED ₄₁ , R ₄₁ , RE
D ₄₂ and R _{46 to} R ₄₈ are preferably substituted, and further, all of the general formulas (A) to (F), and RED _{11 to} RED _42.
Is more preferably substituted. Preferred spectral sensitizing dyes are spectral sensitizing dyes typically used in color sensitizing techniques, such as cyanine dyes, complex cyanine dyes, merocyanine dyes, complex merocyanine dyes,
Includes homopolar cyanine dyes, styryl dyes, and hemicyanine dyes. Representative spectral sensitizing dyes are disclosed in Research Disclosure, Item 36544, September 1994. The research disclosure,
Or FM Hamer's The Cyanine dyes and Related Co
mpounds (Interscience Publishers, New yprk, 1964)
Those skilled in the art can synthesize these dyes by the procedure described in. Further, all the dyes described on pages 7 to 14 of JP-A No. 11-95355 (US Pat. No. 6,054,260) are applicable as they are.

The compounds of types 1 to 4 of the present invention preferably have a total carbon number of 10 to 60. It is more preferably 10 to 50, still more preferably 11 to 40, and particularly preferably 12 to 30.

The compounds of types 1 to 4 of the present invention are oxidized by exposure to a silver halide photographic light-sensitive material using the compound to one electron, and after the subsequent reaction, one electron, or depending on the type. Two or more electrons are emitted and oxidized, and the oxidation potential of the first electron is preferably about 1.4 V or less, more preferably 1.0 V or less. This oxidation potential is preferably above 0V, more preferably above 0.3V. Therefore, the oxidation potential is preferably about 0 to about 1.4 V, more preferably about 0.3 to about 1.
It is in the range of 0V.

Here, the oxidation potential can be measured by the technique of cyclic voltammetry. Specifically, a sample is acetonitrile: water (containing 0.1 M lithium perchlorate) = 80.
%: Dissolved in 20% (volume%) solution and bubbled with nitrogen gas for 10 minutes, then glassy carbon disk was used as working electrode, platinum wire was used as counter electrode, and refer to calomel electrode (SCE) Used for electrodes, at 25 ℃, 0.1
It is measured at a potential scanning speed of V / sec. The oxidation potential vs. SCE is taken at the peak potential of the cyclic voltammetry wave.

When the compounds of types 1 to 4 according to the present invention are one-electron-oxidized compounds and release one more electron after the subsequent reaction, the oxidation potential of the latter stage is preferably -0.5 V to-. 2V, more preferably -0.7V
~ 2V, more preferably -0.9V to -1.6.
V.

When the compounds of types 1 to 4 of the present invention are one-electron-oxidized compounds, which after the subsequent reaction release two or more electrons and are further oxidized, the oxidation potential of the latter stage is as follows. There is no particular limitation. This is because the oxidation potential of the second electron and the oxidation potential of the third and subsequent electrons cannot be clearly distinguished, and therefore it is often difficult to actually measure and distinguish them accurately.

Specific examples of the compounds of types 1 to 4 of the present invention are listed below, but the present invention is not limited thereto.

[0127]

[Chemical 35]

[0128]

[Chemical 36]

[0129]

[Chemical 37]

[0130]

[Chemical 38]

[0131]

[Chemical Formula 39]

[0132]

[Chemical 40]

The compounds of types 1 to 4 of the present invention are described in Japanese Patent Application Nos. 2001-234075 and 2001-23, respectively.
No. 4048 and Japanese Patent Application No. 2001-250679,
It is the same as the compound described in detail. The specific compound examples described in these patent application specifications can also be mentioned as specific examples of the compounds of types 1 to 4 of the present invention.

Next, the compound of type 5 will be described.
The compound of type 5 is represented by XY, in which X represents a reducing group and Y represents a leaving group, and a 1-electron oxidant produced by one-electron oxidation of the reducing group represented by X is , XY continues
It is a compound capable of leaving Y along with a bond cleavage reaction to generate an X radical, and further releasing another electron therefrom. The reaction when such a type A compound is oxidized can be represented by the following formula.

[0135]

[Chemical 41]

The compound of type 5 preferably has an oxidation potential of 0 to 1.4 V, more preferably 0.3 V to
It is 1.0V. The oxidation potential of the radical X · generated in the above reaction formula is preferably −0.7V to −2.0V, and more preferably −0.9V to −1.6V.

Compounds of type 5 preferably have the general formula
It is represented by (G). General formula (G)

[Chemical 42]

In the general formula (G), RED ₀ represents a reducing group, L ₀ represents a leaving group, and R ₀ and R ₁ represent a hydrogen atom or a substituent. RED ₀ and R ₀ , and R ₀ and R ₁ may combine with each other to form a ring structure. RED
₀ represents a group having the same meaning as RED _{12 in} formula (B), and the preferred range is also the same. R ₀ and R ₁ have the same meaning as R ₂₁ and R _{22 in} formula (C), and their preferable ranges are also the same. Provided that R ₀ and R ₁ are, except for a hydrogen atom,
It does not represent a group having the same meaning as L ₀ . RED ₀ and R ₀ may be bonded to each other to form a ring structure, and as an example of the ring structure, RED ₂ and R ₂₁ of the general formula (C) are linked to form a ring structure. The same examples as in the case are mentioned, and the preferable ranges are also the same. Examples of the ring structure formed by combining R ₀ and R ₁ with each other include a cyclopentane ring and a tetrahydrofuran ring. The leaving group represented by L ₀ in the general formula (G) means a carboxy group or a salt thereof, a silyl group, a stannyl group, a germyl group, a triarylboron atom anion, —C (R ₀ ) (R ₁ ) — RED
Represents ₀ group or a hydrogen atom. Among them, the carboxy group or its salt and the silyl group are represented by the general formula (A)
L ₁₁ has the same meaning and its preferable range is also the same.
The stannyl group is preferably a trialkylstannyl group, the germyl group is preferably a trialkylgermyl group, the triarylboron atom anion is preferably a triphenylboron atom anion, wherein the phenyl group has a substituent. Good. L ₀ is “-C (R ₀ ) (R ₁ ).
When the “RED ₀ group” is represented, the compound represented by the general formula (G) means a bis type compound in which —C (R ₀ ) (R ₁ ) —RED ₀ groups are bonded to each other. The leaving group represented by L ₀ in G) is preferably a carboxy group or a salt thereof, a silyl group, a —C (R ₀ ) (R ₁ ) -RED ₀ group, and more preferably a carboxy group or a group thereof. A salt and a hydrogen atom.

When L ₀ represents a hydrogen atom, the compound represented by the general formula (G) preferably has a basic moiety in the molecule. By the action of this base, the compound represented by the general formula (G) is oxidized, and then the hydrogen atom represented by L ₀ is deprotonated to give “RED ₀ (R ₀ ) (R ₁ ) C. A radical represented by "is given, and one electron is emitted from this radical. The base here specifically means a pKa of about 1 to about 10.
Is a conjugate base of an acid showing. For example, nitrogen-containing heterocycles
(Pyridines, imidazoles, benzimidazoles, thiazoles, etc.), anilines, trialkylamines, amino groups, carbonic acids (active methylene anions, etc.), thioacetic acid anion, carboxylate (--CO
O ^-), sulfate (-SO ₃ ^-), or amine oxide
(> N ⁺ (O ⁻ ) −) and the like. It is preferably a conjugate base of an acid having a pKa of about 1 to about 8, more preferably carboxylate, sulfate, or amine oxide, particularly preferably carboxylate. When these bases have an anion, they may have a counter cation,
Examples thereof are the same as those described as the counter ion forming a salt when L ₀ represents a carboxy group or a salt thereof. The position at which these base moieties are bonded may be any of RED ₀ , R ₀ and R ₁ of the general formula (G), but is preferably R ₁ , and for example, a preferred R ₁ group when the base represents a carboxylate. examples of, - (CH _{2)
^{3 -COO -, - (CH 2}} ) 2 -COO -, -CH 2 -COO -
Groups such as.

The compound represented by the general formula (G) is "a compound having an adsorptive group to silver halide in the molecule" or "having a partial structure of a spectral sensitizing dye in the molecule". Preferably, it is a “compound”. More preferably, it is a "compound having an adsorptive group for silver halide in the molecule".

As the adsorptive group to the silver halide contained in the compound represented by the general formula (G), types 1 to 4 of the present invention can be used.
Examples thereof include the same adsorptive groups that the compound (1) may have, and in addition, selenooxo groups (-C = Se-), telluroxo groups (-C = Te-), seleno groups ( -Se-), a telluro group (-Te-), or an active methine group is mentioned. Here, a selenooxo group (-C
= Se-) and a telluroxo group (-C = Te-),
It is a Se or Te derivative of a compound having a thione group (-C = S-), and as described for the thione group, a selenoamide group (-C = Se-NH-) or a telluramide group (-C = Te-NH-). Group may be included.
The seleno group (-Se-) and the telluro group (-Te-) are Se or Te derivatives of a compound also having a sulfide group (-S-), and a Se or Te substitution product of a compound having a sulfide group. Can be cited as an example. The active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group is an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group. Group, arylsulfonyl group, sulfamoyl group, trifluoromethyl group, cyano group, nitro group, imino group. Here, the two electron-withdrawing groups may be bonded to each other to form a cyclic structure.

The adsorption promoting group contained in the compound represented by the general formula (G) is preferably a mercapto group (or a salt thereof), a thione group (-C = S-), a nitrogen atom, a sulfur atom, a selenium atom and tellurium. A heterocyclic group containing at least one atom selected from the group consisting of atoms and a sulfide group, more preferably a mercapto-substituted nitrogen-containing heterocyclic group, a dimercapto-substituted heterocyclic group, or -NH capable of forming iminosilver (> NAg). A nitrogen-containing heterocyclic group having a group as a partial structure of the heterocycle, and these are the same as those described for the preferable range of the adsorptive group that the compounds of types 1 to 4 may have. The adsorptive group may be substituted anywhere in the general formula (G), but is preferably R
It is preferably substituted with ED ₀ or R ₀ , more preferably RED ₀ .

The partial structure of the spectral sensitizing dye which the compound represented by the general formula (G) may have means the type 1 of the present invention.
It is the same as the partial structure of the spectral sensitizing dye that the compound of 4 to 4 may have.

Specific examples of the compound represented by formula (G) are shown below, but the invention is not limited thereto.

[Chemical 43]

[0145]

[Chemical 44]

[0146]

[Chemical formula 45]

Specific examples of the compound represented by the general formula (G) include the compounds PMT-1 to S-3 described in JP-A 9-211769 (Table E and Table F on pages 28 to 32).
7), JP-A-9-21174, and JP-A-11-953.
No. 55 (Compounds INV1-36), Special Table 2001-500
No. 996 (Compounds 1-74, 80-87, 92-12)
2), US Pat. No. 5,747,235, US Pat.
47,236, European Patent 786692A1 (Compounds INV1 to 35), European Patent 893732A1, US Patent 6,054,260, US Patent 5,994,05.
Examples of the compounds referred to as "one-photon two-electron sensitizers" or "deprotonated electron-donating sensitizers" described in patents such as No. 1 are mentioned as they are.

The compounds of types 1 to 5 of the present invention may be used at any time during the preparation of emulsions and the process of producing a light-sensitive material. For example, during grain formation, desalting step, during chemical sensitization, before coating and the like. It is also possible to add them in multiple times during these steps. The addition position is preferably from the end of grain formation to before the desalting step, at the time of chemical sensitization (immediately before the start of chemical sensitization to immediately after the end), and before coating, and more preferably at the time of chemical sensitization and before coating.

The compounds of types 1 to 5 of the present invention are preferably added by dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is raised or lowered may be dissolved by raising or lowering the pH and then added.

The compounds of types 1 to 5 of the present invention are preferably used in the emulsion layer, but they may be added to the protective layer or the intermediate layer together with the emulsion layer and diffused during coating. The compound of the present invention may be added before or after the sensitizing dye, preferably 1 × 10 ⁻⁹ to 1 mol per mol of silver halide.
5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 × 10
^-3 mol is contained in the silver halide emulsion layer.

Next, the compound represented by formula (I) of the present invention will be explained.

General formula (I)

[Chemical formula 46]

In the general formula (I), R ²¹ represents a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group represented by R ²¹ may have a straight chain structure, a branched chain structure, or a cyclic structure. As the substituent, any substituent may be used, but an alkenyl group, an aryl group, an alkoxy group, a halogen atom (preferably C
1), a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, a phosphoric acid ester group and the like are preferable. R ²¹ preferably has no fluorine as a substituent, more preferably an unsubstituted alkyl group. R ²¹ is
The carbon number is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more. The upper limit of the carbon number of R ²¹ is preferably 24.

R _af represents a perfluoroalkylene group.
Here, the perfluoroalkylene group refers to a group in which all hydrogen atoms of the alkylene group are fluorine-substituted. The perfluoroalkylene group may be linear or branched, and may have a cyclic structure. R
_af preferably has 10 or less carbon atoms, and more preferably 8 or less carbon atoms. The lower limit of the carbon number of Raf is preferably 1.

W ² represents a hydrogen atom or a fluorine atom, preferably a fluorine atom. L _a represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. The substituents are preferably those listed for R ²¹ . L _a preferably has 4 or less carbon atoms, and L a
The lower limit of the carbon number of a is preferably 1. Further, it is preferably an unsubstituted alkylene.

One of A ² and B ² represents a hydrogen atom and the other represents —L _b —SO ₃ M, and M represents a cation. Here, as the cation represented by M, for example, an alkali metal ion (lithium ion, sodium ion, potassium ion and the like), alkaline earth metal ion (barium ion, calcium ion and the like), ammonium ion and the like are preferably exemplified. . Of these, lithium ion, sodium ion, potassium ion or ammonium ion is more preferable, and lithium ion, sodium ion or potassium ion is more preferable, and the total carbon number and substituents of the compound of the general formula (I), It can be appropriately selected depending on the degree of branching of the alkyl group. R ^21, L _a and R when the total 16 or more carbon atoms of _af, it is excellent in terms of solubility (in particular with respect to water) compatibility between antistatic property or coating uniformity is a lithium-ion .

L _b represents a single bond or a substituted or unsubstituted alkylene group. The substituent is preferably those listed R ^{2 1.} When L _b is an alkylene group, the C number is preferably 2 or less, preferably unsubstituted, and more preferably a methylene group. Most preferably, L _b is a single bond.

It is more preferable that the above general formula (I) is a combination of the above respective preferable embodiments. The general formula (I) is preferably further represented by the following general formula (Ia). General formula (Ia)

[Chemical 47]

In the above general formula (Ia), R ²² represents a substituted or unsubstituted alkyl group having 6 or more carbon atoms in total. However,
R ²² does not become an alkyl group substituted with a fluorine atom. The substituted or unsubstituted alkyl group represented by R ²² may have a straight chain structure, a branched chain structure, or a cyclic structure. As the substituent, an alkenyl group, an aryl group, an alkoxy group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group,
Examples thereof include a carbamoyl group, an oxycarbonyl group, and a phosphoric acid ester group.

The substituted or unsubstituted alkyl group represented by R ²² preferably has 6 to 24 total carbon atoms. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include:
n-hexyl group, n-heptyl group, n-octyl group, t
ert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-
Hexyldecyl group, octadecyl group, eicosyl group, 2
-Octyldodecyl group, docosyl group, tetracosyl group,
Examples thereof include 2-decyltetradecyl group, tricosyl group, cyclohexyl group, cycloheptyl group and the like. Preferred examples of the substituted alkyl group having a total carbon number of 6 to 24, including the carbon atoms of the substituents, include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group, 2- Methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) An ethyl group etc. can be mentioned.

The substituted or unsubstituted alkyl group represented by R ²² more preferably has 6 to 18 carbon atoms in total.
Preferred examples of the unsubstituted alkyl group having 6 to 18 carbon atoms include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3- Trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-
Hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like can be mentioned. In addition, preferred examples of the substituted alkyl group having a total carbon number of 6 to 18 including the carbon number of the substituent include a phenethyl group, a 6-phenoxyhexyl group, a 12-phenyldodecyl group, an oleyl group, a linoleyl group and a linolenyl group. Is mentioned. Among them, R ¹
As, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n
-Nonyl group, 1,1,3-trimethylhexyl group, n-
A decyl group, an n-dodecyl group, a cetyl group, a hexadecyl group, a 2-hexyldecyl group, an octadecyl group, an oleyl group, a linoleyl group, and a linolenyl group are more preferable, and a straight chain, cyclic or branched group having 8 to 16 carbon atoms Is particularly preferably an unsubstituted alkyl group.

In the general formula (Ia), R _f has 6 carbon atoms.
The following perfluoroalkyl groups are represented. Here, the perfluoroalkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with fluorine. The alkyl group in the perfluoroalkyl group may be linear or branched, and may have a cyclic structure. Examples of the perfluoroalkyl group represented by R _f include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, a nonafluoro-n-butyl group, and an undecafluoro-group.
n-pentyl group, tridecafluoro-n-hexyl group,
Undecafluorocyclohexyl group and the like can be mentioned. Among them, a perfluoroalkyl group having 2 to 4 carbon atoms (eg, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group, etc.) is preferable, and heptafluoro-n
-Propyl group and nonafluoro-n-butyl group are particularly preferable.

In the general formula (Ia), n represents an integer of 1 or more. It is preferably an integer of 1 to 4, and particularly preferably 1 or 2. As a combination of n and R _f , when n = 1, R _f is a heptafluoro-n-propyl group or a nonafluoro-n-butyl group, and when n = 2, R _f is a nonafluoro-n-butyl group. More preferably, it is a group.

In the above general formula (Ia), X ²¹ and X ²²
Is a hydrogen atom and the other is SO ₃ M,
Represents a cation. Here, as the cation represented by M, for example, an alkali metal ion (lithium ion, sodium ion, potassium ion and the like), alkaline earth metal ion (barium ion, calcium ion and the like), ammonium ion and the like are preferably exemplified. . Of these, lithium ion, sodium ion, potassium ion or ammonium ion is particularly preferable.

Specific preferred examples of the fluorine compound represented by the general formula (I) are shown below, but the invention is not limited to the following specific examples. In addition,
Hereinafter, for the sake of convenience, X ²¹ is SO ₃ M and X ²² is an exemplary compound. However, in the following exemplary compound, X ²¹ may be a hydrogen atom and X ²² may be SO ₃ M. Also, those compounds can be mentioned as specific examples of the fluorine compound of the present invention.

Unless otherwise specified, in the structural description of the exemplified compounds below, an alkyl group and a perfluoroalkyl group mean a linear structure. Furthermore, among the abbreviations in the structural notation,
The groups with the symbols 2EH and 2BO represent the groups shown below.

2EH: 2-ethylhexyl 2BO: 2-butyloctyl

[Chemical 48]

[0168]

[Chemical 49]

[0169]

[Chemical 50]

[0170]

[Chemical 51]

[0171]

[Chemical 52]

[0172]

[Chemical 53]

[0173]

[Chemical 54]

The fluorine compounds represented by the above general formulas (I) and (Ia) can be easily synthesized by combining general esterification reaction and sulfonation reaction.

The compound represented by formula (II) of the present invention will be described. General formula (II)

[Chemical 55]

In the formula, A ³ and B ³ each independently represent a fluorine atom or a hydrogen atom. a and b each independently represent an integer of 1 to 6. c and d each independently represent an integer of 4 to 8. x represents 0 or 1. M represents a cation.

In the general formula (II), A³, B³Are independent
Represents a fluorine atom or a hydrogen atom, and A³, B³Is the same
Or it may be different. A³, B³As preferred
Is A ³, B³Both are fluorine atoms or hydrogen atoms,
More preferably A³, B³Both are fluorine atoms.

A and b each independently represent an integer of 1 to 6. a and b may be different from each other or the same as long as they are integers of 1 to 6. a and b are preferably integers of 1 to 6 and a = b, more preferably integers of 2 or 3 and a = b, and further preferably a = b = 2.

C and d each independently represent an integer of 4 to 8. c and d may be different from each other or the same as long as they are integers of 4 to 8. c and d are preferably integers of 4 to 6 and a = b, more preferably integers of 4 or 6 and a = b, and further preferably a = b = 4. x represents 0 or 1, both of which are likewise preferred.

M represents a cation, and examples of the cation represented by M include an alkali metal ion (lithium ion, sodium ion, potassium ion, etc.), an alkaline earth metal ion (barium ion, calcium ion, etc.), and an ammonium ion. Etc. are preferably applied. Among these, lithium ion, sodium ion, potassium ion, and ammonium ion are particularly preferable.

The general formula (II) is more preferably the following general formula (II-a). General formula (II-a)

[Chemical 56]

In the formula, a, b, c, d, M and x are represented by the general formula (I
It has the same meaning as those in I) and the preferred range is also the same.

The general formula (II) is more preferably the following general formula (II-b). General formula (II-b)

[Chemical 57]

Where a¹Represents an integer of 2 to 3. c¹
Represents an integer of 4 to 6. M represents a cation. a¹Is
Represents an integer of 2 to 3, a¹Is preferably 2
It c ¹Represents an integer of 4 to 6, and c¹As preferred
Is 4. x represents 0 or 1, both of which are equally good
Good

Specific examples of preferred surfactants used in the present invention are shown below, but the present invention is not limited to these specific examples.

[0186]

[Chemical 58]

[0187]

[Chemical 59]

[0188]

[Chemical 60]

[0189]

[Chemical formula 61]

The surfactants represented by the above general formulas (II), (II-a) and (II-b) of the present invention can be easily synthesized by combining general esterification reaction and sulfonation reaction. Is.

Next, the compound represented by formula (III) of the present invention will be explained. General formula (III)

[Chemical formula 62]

In the general formula (III), R ¹ and R ² each represent a substituted or unsubstituted alkyl group, but at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom. R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, X ⁴¹ , X ⁴² and Z each independently represent a divalent linking group, and M ⁺ represents a cationic substituent. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1.

In the general formula (III), R ¹ and R ² each represent a substituted or unsubstituted alkyl group. The alkyl group has 1 or more carbon atoms and may be linear, branched or cyclic. Examples of the substituent include a halogen atom, an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, and a phosphoric acid ester group. However, R
^At least one of ¹ and R ² represents an alkyl group substituted with a fluorine atom (hereinafter, the alkyl group substituted with a fluorine atom is referred to as “Rf”).

Rf is an alkyl group having 1 or more carbon atoms and substituted with at least one fluorine atom, and Rf may be substituted with at least one fluorine atom, and may be linear, branched or cyclic. The structure may be.
Further, it may be further substituted with a substituent other than a fluorine atom, or may be substituted only with a fluorine atom. R
As the substituent of f other than the fluorine atom, an alkenyl group,
Examples thereof include an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group and a phosphoric acid ester group.

Rf is preferably a fluorine-substituted alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 4 to 10 carbon atoms. Preferred examples of _{Rf, - (CH 2) n1} - (CF 2) in _{m @ 2} -E (wherein,
n1 = 1 to 6 integer, m2 = 3 to 10 integer, E = H or F), and more preferable examples

[Chemical formula 63] And so on.

More preferably, Rf is a tri-terminal.
Alky having 4 to 10 carbon atoms substituted with a fluoromethyl group
Group, particularly preferably-(CH₂)_n1-(CF₂)
_n2It is an alkyl group having 3 to 10 carbon atoms represented by F (n
¹Represents an integer of 1 to 6. n²Represents an integer of 3 to 8).
Specifically, -CH₂-(CF₂)₂F,-(CH₂)₆−
(CF₂)_FourF,-(CH₂)₃-(CF₂)_FourF, -CH₂
-(CF₂)₃F,-(CH₂)₂-(CF₂)_FourF,-(C
H₂)₃-(CF₂)_FourF,-(CH₂)₆-(CF ₂)_FourF,
-(CH₂)₂-(CF₂)₆F,-(CH₂)₃-(C
F₂)₆F,-(CH ₂)₂-(CF₂)₆F etc.
It Among these, in particular,-(CH₂)₂-(CF₂)_Four
F and-(CH₂)₂-(CF₂)₆F is most preferred.

In the general formula (III), it is preferable that both R ¹ and R ² represent Rf.

When R ¹ and R ² each represent an alkyl group other than Rf, that is, an alkyl group not substituted with a fluorine atom, the alkyl group may be a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms. , And more preferably a substituted or unsubstituted alkyl group having 6 to 24 carbon atoms. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include:
n-hexyl group, n-heptyl group, n-octyl group, t
ert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-
Hexyldecyl group, octadecyl group, eicosyl group, 2
-Octyldodecyl group, docosyl group, tetracosyl group,
Examples thereof include 2-decyltetradecyl group, tricosyl group, cyclohexyl group, cycloheptyl group and the like. Further, preferred examples of the alkyl group having 6 to 24 total carbon atoms having a substituent include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group,
2-methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-
Phenyl dodecyl group, 18-phenyl octadecyl group,
Examples thereof include a 12- (p-chlorophenyl) dodecyl group and a 2- (diphenylphosphate) ethyl group.

The alkyl group other than Rf represented by R ¹ and R ² is more preferably C 6-18.
Is a substituted or unsubstituted alkyl group. 6 to 1 carbon atoms
Preferred examples of the unsubstituted alkyl group of 8 include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,
1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like can be mentioned. Preferred examples of the substituted alkyl group having a total carbon number of 6 to 18 having a substituent include a phenethyl group, a 6-phenoxyhexyl group, and a 12-
Examples thereof include a phenyldodecyl group, an oleyl group, a linoleyl group and a linolenyl group.

The alkyl group other than Rf represented by R ¹ and R ² is particularly preferably n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-hexyl group. Nonyl group, 1,1,3
-Trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, oleyl group, linoleyl group, linolenyl group, most preferably having 8 to 16 carbon atoms. It is a linear, cyclic or branched unsubstituted alkyl group.

In the general formula (III), R ³ , R ⁴ and R ⁵
Each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 carbon atom).
To 20, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, for example, methyl group, ethyl group, isopropyl group, tert-butyl group,
n-octyl group, n-decyl group, n-hexadecyl group,
A cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like), an alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, and particularly preferably a carbon number of 2 to 8). , Vinyl group, allyl group, 2-butenyl group, 3-pentenyl group and the like), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). An alkynyl group of, for example, a propargyl group, a 3-pentynyl group and the like), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms). An aryl group, for example, a phenyl group, a p-methylphenyl group, a naphthyl group and the like), a substituted or unsubstituted amino group ( It is preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, Dibenzylamino group and the like), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms,
An alkoxy group having 1 to 8 carbon atoms is particularly preferable, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group, and an aryloxy group (preferably having a carbon number of 6 to 2).
0, more preferably an aryloxy group having 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group, and an acyl group (preferably having a carbon number). 1 to 20, more preferably 1 to 16 carbon atoms, and most preferably 1 to 12 carbon atoms.
An acyl group, for example, an acetyl group, a benzoyl group,
Formyl group, pivaloyl group and the like), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 1 carbon atoms).
2 is an alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably carbon atoms). 7 to 10 aryloxycarbonyl groups, for example, phenyloxycarbonyl group and the like), acyloxy groups (preferably having 2 to 20 carbon atoms,
More preferably, it is an acyloxy group having 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2 to 20 carbon atoms, and more preferably Is an acylamino group having 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group. An alkoxycarbonylamino group (preferably 2 to 20 carbon atoms, more preferably Is an alkoxycarbonylamino group having 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms). Preferably, it has 7 to 16 carbon atoms, particularly preferably 7 to 1 carbon atoms.
2 is an aryloxycarbonylamino group, and examples thereof include a phenyloxycarbonylamino group and the like, and a sulfonylamino group (preferably having 1 to 2 carbon atoms).
0, more preferably a sulfonylamino group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group, and a sulfamoyl group (preferably having a carbon number). It is a sulfamoyl group having 0 to 20, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group. A carbamoyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, and particularly preferably a carbon number of 1 to 12).
Unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like), alkylthio group (preferably having 1 to 2 carbon atoms)
0, more preferably an alkylthio group having 1 to 16 carbon atoms, and particularly preferably an alkylthio group having 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group. An arylthio group (preferably 6 to 20 carbon atoms) is more preferable. It is preferably an arylthio group having 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group and the like, and a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms). 16, particularly preferably 1 to 1 carbon atoms
A sulfonyl group having 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). Group, for example, a methanesulfinyl group, a benzenesulfinyl group, etc.), a ureido group (preferably having a carbon number of 1 to 1).
20, more preferably a ureido group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an unsubstituted ureido group, a methylureido group, a phenylureido group, and the like, and a phosphoramide group. (Preferably a phosphoric acid amide group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms;
Diethylphosphoric acid amide group, phenylphosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group Group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 12 heterocyclic groups, for example, heterocyclic groups having a hetero atom such as nitrogen atom, oxygen atom, sulfur atom, for example, imidazolyl group, pyridyl group, quinolyl group, furyl group. , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably, A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

Each of R ³ , R ⁴ and R ⁵ is preferably an alkyl group or a hydrogen atom, more preferably a hydrogen atom.

In the above formula, X⁴¹And X⁴²Each is divalent
Represents a linking group of. There is no particular limitation as long as it is a divalent linking group
Is preferably an arylene group, -O-, -S- or-.
NR ³¹-(R³¹Represents a hydrogen atom or a substituent. Substituent
As R³, R^FourAnd R^FiveIs the same as the example of the substituent represented by
is there. -R³¹Is preferably an alkyl group or the aforementioned R
f or a hydrogen atom, more preferably a hydrogen atom.
Or a group obtained by combining them.
And more preferably -O-, -S- or -NR³¹And
It X⁴¹And X⁴²More preferably as -O-
Is -NR³¹-, More preferably -O- or -N
H-, particularly preferably -O-.

In the above formula, Z represents a divalent linking group. Bivalent
There is no particular limitation as long as it is a linking group, but it is preferably alkyle.
Group, arylene group, -C (= O)-, -O-, -S
-, -S (= O)-, -S (= O)₂-Or-NR³²
-(R³²Represents a hydrogen atom or a substituent, and as a substituent
Is R³, R^FourAnd R^FiveIt is the same as the example of the substituent represented by.
R³²Is preferably an alkyl group or a hydrogen atom
And more preferably a hydrogen atom) alone or
It is a group obtained by combining these, more preferably the number of carbon atoms
An alkylene group having 1 to 12 and an arylene having 6 to 12 carbon atoms
Group, -C (= O)-, -O-, -S-, -S (= O)
-, -S (= O)₂-Or-NR³²− Alone or
A group obtained by combining these (in the case of combining, M⁺When
The group to be bonded is preferably an alkylene group. ). Z and
And more preferably, an alkylene group having 1 to 8 carbon atoms,
C (= O)-, -O-, -S-, -S (= O)-, -S
(= O) ₂-Or-NR³²− Alone or in pairs
Groups obtained together, for example,

[Chemical 64] And the like (in the formula, the left bond is bonded to M ⁺ ).

In the above formula, M ⁺ represents a cationic substituent, and M ⁺ is preferably an organic cationic substituent, more preferably a nitrogen or phosphorus cationic group. A pyridinium cation or an ammonium cation is more preferable, and a trialkylammonium cation represented by the following general formula (IV) is more preferable. General formula (IV)

[Chemical 65]

In the above formula, R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group. As the substituent, those mentioned as the substituents of R ³ , R ⁴ and R ⁵ can be applied. If possible, R ¹³ , R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. R
¹³ , R ¹⁴ and R ¹⁵ preferably have 1 to 12 carbon atoms.
Is an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group, an ethyl group,
It is a methylcarboxyl group, and particularly preferably a methyl group.

In the above formula, Y ⁻ represents a counter anion, which may be an inorganic anion or an organic anion. Further, when the charge becomes 0 in the molecule, Y ⁻ may be omitted. The inorganic anion is preferably iodine ion, bromine ion, chlorine ion or the like, and the organic anion is preferably,
Examples thereof include p-toluenesulfonate ion and benzenesulfonate ion. Y ⁻ is more preferably an iodine ion, a p-toluenesulfonic acid ion or a benzenesulfonic acid ion, and further preferably a p-toluenesulfonic acid.

In the above formula, m represents 0 or 1, preferably 0.

Among the compounds represented by the above general formula (III), the compound represented by the following general formula (III-a) is preferable. General formula (III-a)

[Chemical formula 66]

In the formula, R¹¹And R⁴¹Respectively replace or
Represents an unsubstituted alkyl group, but R ¹And R⁴¹Little
At least one represents an alkyl group substituted with a fluorine atom.
And R^{1 1}And R⁴¹Has a total carbon number of 19 or less.
R¹³, R¹⁴And R¹⁵Are independently replaced or absent
Represents a substituted alkyl group and is bonded to each other to form a ring.
May be. X⁴¹And X⁴²Are independently -O-,-
S- or -NR³¹Represents-, R³¹Is a hydrogen atom or
Represents a substituent, and Z represents a divalent linking group. Y^-Is anio
Represents Y. When the charge in the molecule becomes 0, Y^-Flower
You don't have to. Where Z and Y^-Is the above general formula
It has the same meaning as those in (IV) and the preferred range is also the same.
It is like. R¹³, R¹⁴And R¹⁵For each
It has the same meaning as those in the above general formula (III) and is preferable.
The same applies to the new range.

Among the compounds represented by the above general formula (III), the compounds represented by the following general formula (III-b) are preferable.

[Chemical formula 67]

In the formula, R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group, which may be bonded to each other to form a ring. Z represents a divalent linking group, and A and B each represent a fluorine atom or a hydrogen atom. n ¹ represents an integer of ¹ to 6, and n ² represents an integer of 3 to 8. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. In the formula, Z and Y ⁻ have the same meanings as those in formula (III), and the preferred ranges are also the same. R ¹³ , R ¹⁴ and R ¹⁵
Are synonymous with those in the general formula (III), and the preferred ranges are also the same. A and B are preferably fluorine atoms.

Among the compounds represented by the above general formula (III), the compound represented by the following general formula (III-c) is more preferable.

[0214]

[Chemical 68]

In the formula, n ¹ is an integer of ¹ to 6 and n ² is 3 to 8.
2 (n ¹ + n ² ) is 19 or less.
R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group, which may be bonded to each other to form a ring. X ⁴³ and X ⁴⁴ are independently -O-,-
S- or -NR ³¹ - represents a. R ³¹ represents a hydrogen atom or a substituent, and Z represents a divalent linking group. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. In the formula, Z and Y ⁻ have the same meanings as those in formula (III), and the preferred ranges are also the same. For R ^13, R ^{1 4} and R ¹⁵ are each have the same meanings as those in formula (III), and preferred ranges are also the same.

N ¹ represents an integer of ¹ to 6, preferably 1
Represents an integer of 3 to 3, more preferably 2 or 3,
Most preferably it is 2. n ² represents an integer of 3 to 8,
It is more preferably 3 to 6, and even more preferably 4 to 6.
Is. As a preferable combination of n ¹ and n ² ,
It is preferred that n ¹ is 2 or 3 and n ² is 4 or 6.

Specific examples of the compounds represented by the above general formula (III) are shown below, but the present invention is not limited to the following specific examples. In the structural description of the exemplified compounds below, unless otherwise specified, an alkyl group and a perfluoroalkyl group mean a linear structure. Moreover, 2EH of the abbreviations in the notation means 2-ethylhexyl.

[0218]

[Chemical 69]

[0219]

[Chemical 70]

[0220]

[Chemical 71]

[0221]

[Chemical 72]

[0222]

[Chemical formula 73]

[0223]

[Chemical 74]

[0224]

[Chemical 75]

[0225]

[Chemical 76]

[0226]

[Chemical 77]

[0227]

[Chemical 78]

[0228]

[Chemical 79]

[0229]

[Chemical 80]

Next, the above general formulas (III) and (III
Examples of general methods for synthesizing the compounds represented by formulas (a), (III-b), and (III-c) are shown below, but the invention is not limited thereto.

The compound of the present invention can be synthesized using a fumaric acid derivative, a maleic acid derivative, an itaconic acid derivative, a glutamic acid derivative, an aspartic acid derivative and the like as raw materials.
For example, when a fumaric acid derivative, a maleic acid derivative or an itaconic acid derivative is used as a raw material, it can be synthesized by subjecting their double bond to a Michael addition reaction with a nucleophilic species and then cationization with an alkylating agent. .

In the present invention, the general formulas (I), (II),
The compound (III) may be used alone,
Each may use multiple different compounds simultaneously,
The amount used is preferably 10 ^-6 mol to 10 ^-1 mol / m ² . Moreover, you may use together the other surfactant with the compound of this invention. Examples of the surfactant that can be used in combination include various anionic, cationic and nonionic surfactants. The surfactant used in combination may be a polymer surfactant or a fluorine-based surfactant other than the compound of the present invention. Examples of the surfactant that can be used in combination include, for example, JP-A-62-215272 (6
47-706), Research Disclosure (R
D) Items 17643, 26-27 (1978, 1
February), p. 18716, 650 (November 1979),
307105, pages 875-876 (November 1989)
Monthly) and the like.

As another component which can be used in combination, a polymer compound can be mentioned as a typical example. The polymer compound may be a polymer soluble in an aqueous medium (hereinafter referred to as “soluble polymer”) or an aqueous dispersion of polymer (so-called polymer latex).
The soluble polymer is not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the like. Polymer latex includes various vinyl monomers [eg, acrylates. Derivative, methacrylate derivative, acrylamide derivative, methacrylamide derivative,
Styrene derivative, conjugated diene derivative, N-vinyl compound, O-vinyl compound, vinyl nitrile, other vinyl compound (eg ethylene, vinylidene chloride)] homopolymer or copolymer, dispersion of condensation polymer (eg polyester, polyurethane) , Polycarbonate, polyamide). Specific examples of this type of polymer compound are described in, for example, JP-A-62-21527.
No. 2 (pages 707 to 763), Research Disclosure (RD) Items 17643, 651 (197).
December 1988), p. 18716, 650 (1 1979)
Jan., 307105, pp. 873-874 (1989).
Polymer compounds described in (November, 2013) and the like.

In the present invention, the compounds represented by the general formulas (I) and (I
The compounds I) and (III) are preferably used as a surfactant in a coating composition for forming a layer (particularly, a protective layer, an undercoat layer, a back layer, etc.) constituting a silver halide photographic light-sensitive material. Used. Among them, it is particularly preferable to use for forming the hydrophilic colloid layer of the uppermost layer of the photographic light-sensitive material, since it is possible to obtain effective antistatic ability and coating uniformity, but other layers or intermediate layers having a spectral sensitivity. It may be added to the layer. Further, it may be added to a plurality of layers, or any one layer may be added.

When it is added to the coating composition, it may be dissolved in a medium and then added, or it may be added as a dispersion. For example, water or organic solvents (eg, methanol, ethanol,
Isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, phenoxyethanol, etc.) may be used alone or in combination, and if necessary, the pH may be adjusted and dissolved. Also, the dispersion is
It may be added alone or in the form of a dispersion in which various compounds such as couplers, matting agents and color mixing inhibitors, and silver halide coexist.

General formulas (I), (II) and (III) of the present invention
It is essential that the above compound is contained in a certain amount or more on the surface of the photosensitive material. The amount present on the surface of the photosensitive material is XPS on the surface of the photosensitive material.
(X-ray Photoelectron spec
can be detected by the fluorescent X-ray intensity ratio (F / C) of fluorine and carbon, but F / C is preferably 0.5 or more, more preferably 0.8 or more, Particularly preferably 1.0 or more,
Most preferably, it is 1.5 or more. Preferably F
/ C is 10 or less.

Aqueous coating compositions containing the compounds of the invention include
Other various compounds may be contained depending on the layer used in the light-sensitive material, and they may be dissolved or dispersed in a medium. Examples thereof include various couplers, ultraviolet absorbers, color mixture preventing agents, antistatic agents, scavengers, antifoggants, film hardeners, dyes and antifungal agents. Further, as described above, an aqueous coating composition containing the compound of the present invention is preferably used for forming the hydrophilic colloid layer of the uppermost layer of the photographic light-sensitive material, but in this case, in the coating composition, In addition to the hydrophilic colloid (eg gelatin) and the compound of the present invention, other surfactants, matting agents, sliding agents, colloidal silica, gelatin plasticizers and the like can be contained.

The synthetic examples of the present invention will be specifically described below, but the present invention is not limited to these specific synthetic examples. (Synthesis Example 1 Synthesis of Exemplified Compound FS-8) 1-1 Synthesis of Monooctyl Maleate Maleic anhydride 49 g (0.50 mol), octanol 65 g (0.50 mol), and chloroform
In 200 ml (hereinafter, ml is also referred to as “mL”), 72 ml of triethylamine (0.
(53 mol) was slowly added dropwise while keeping the temperature below 30 ° C. in an ice bath. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, add 400 mL of chloroform, and add 1 mol / L.
The organic phase was washed with hydrochloric acid, and the organic phase was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 114 g of monooctyl maleate as a colorless transparent oily compound.

1-2 Synthesis of maleic acid monooctyl chloride To 104 g (0.5 mol) of phosphorus pentachloride, 114 g (0.5 mol) of monooctyl maleate was slowly added dropwise while keeping the temperature below 30 ° C. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, the mixture was heated to 60 ° C., decompressed with an aspirator, the generated phosphorus oxychloride was distilled off, and a yellow oily compound, monooctyl maleate chloride was added to 113
g (yield 92%) was obtained.

1-3 Maleic acid Mono 3,3,4
Synthesis of 4,5,5,6,6,6-nonafluorohexyl monooctyl 3,3,4,4,5,5,6,6,6-nonafluorohexanol 120 g (0.45 mol), and pyridine 40 0.4 mL (0.50 mol) of chloroform 20
Dissolve in 0 mL, cool in an ice bath, and keep the internal temperature at 20 ° C or less, and then add 113 g of monooctyl chloride maleate.
(0.45 mol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, add 1000 mL of ethyl acetate,
After washing the organic phase with water, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, the organic layer is recovered, the organic solvent is distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 to 6/4) is performed. v /
The purification operation was performed in v) to obtain 139 g (yield: 65%) of the desired product as a colorless transparent oily compound.

1-4 sodium mono 3,3,4,4
5,5,6,6,6-Nonafluorohexyl Synthesis of monooctyl sulfosuccinate (FS-8) Maleic acid Mono 3,3,4,4,5,5,6,6,6
-Nonafluorohexyl monooctyl 139 g (0.
29 mol) and sodium bisulfite 33.5 g
(0.32 mol) and water-ethanol (volume ratio 1 /
1) 140 mL was added and the mixture was heated under reflux for 10 hours. Then, 1000 mL of chloroform was added, the organic phase was washed with a saturated aqueous sodium chloride solution, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, recrystallization was performed with 500 mL of toluene, and crystals were precipitated when cooled in an ice bath. did. Finally, the crystals were separated by filtration to obtain the target compound (FS-
49 g (yield 29%) of 8) was obtained.

Melting point and ¹ H-NMR of the obtained compound
The data are as follows. Melting point: 250-254 ° C. ¹ H-NMR (DMSO-d ₆ ): δ 0.84-0.88
(M, 3H), 1.25 (br, 10H), 1.51
(Br, 2H), 2.56-2.65 (m, 2H),
2.79-2.97 (m, 2H), 3.62-3.69
(M, 1H), 3.97 (br, 2H), 4.30
(M, 2H).

(Synthesis Example 2 Synthesis of Exemplified Compound FS-9) 2-1 Synthesis of Maleic Acid (2-Ethylhexyl) Chloride 4.1 g (20 mmol) of phosphorus pentachloride was added to Aldrich mono (2-ethylhexyl) maleate. 4.5 g (2
(0 mmol) was slowly added dropwise while keeping the temperature below 30 ° C. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then 6
The mixture was heated to 0 ° C., decompressed with an aspirator, the produced phosphorus oxychloride was distilled off, and 4.5 g of a brown oily compound maleic acid (2-ethylhexyl) chloride (yield 9
2%) was obtained.

2-2 Maleic acid Mono 2-ethylhexyl Mono 3,3,4,5,5,6,6,6-Synthesis of nonafluorohexyl 3,3,4,4,5,5,6 5.3 g (20 mmol) of 6,6-nonafluorohexanol and 2.8 mL (20 mmol) of triethylamine were dissolved in 10 mL of chloroform, cooled with an ice bath, and maleic acid (2-ethylhexyl was maintained while keeping the internal temperature at 20 ° C or lower. ) Chloride (4.5 g, 18 mmol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, add ethyl acetate to 50
After addition of mL, the organic phase was washed with water, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, the organic phase was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 to 0/0). 5
/ 5 (volume ratio)) to obtain 4.0 g (yield 46%) of a colorless transparent target compound.

2-3 Sodium mono 2-ethylhexyl mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl sulfosuccinate (FS-9) synthesis Maleic acid mono 2-ethylhexyl mono 3, 3, 4,
4,5,5,6,6,6-nonafluorohexyl
2.5 g (89.6 mmol), 10.2 g (98.0 mmol) of sodium hydrogen sulfite, and 50 mL of water-ethanol (volume ratio 1/1) were added, and the mixture was heated under reflux for 2 hours. After that, 1000 mL of ethyl acetate was added, the organic phase was washed with a saturated aqueous sodium chloride solution, the organic phase was recovered, the organic solvent was distilled off under reduced pressure, and recrystallization operation was performed with 250 mL of toluene, and crystals were obtained by cooling with an ice bath. Precipitated. Finally, the crystals were separated by filtration to obtain 21.7 g (yield 48%) of a colorless and transparent target compound (FS-9).

Melting point and ¹ H-NMR of the obtained compound
The data are as follows. Melting point: 240-244 ° C. ¹ H-NMR (DMSO-d ₆ ): δ 0.82-0.93
(M, 6H), 1.13-1.32 (m, 8H), 1.
50 (br, 1H), 2.57-2.65 (m, 2
H), 2.84-2.98 (m, 2H), 3.63-
3.68 (m, 1H), 3.90 (d, 2H), 4.3
0 (m, 2H).

Synthesis Example 3 Synthesis of Exemplified Compound FS-12 3-1 Synthesis of Monododecyl Maleate Into 49.0 g (0.50 mol) maleic anhydride, 93.2 g (0.50 mol) dodecanol and 210 mL chloroform. , Triethylamine 73.8 mL
(0.53 mol) was slowly added dropwise while keeping the temperature below 30 ° C. in an ice bath. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then add 1000 mL of chloroform and add 1 m
The organic phase was washed with ol / L hydrochloric acid, the organic phase was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to quantitatively obtain monododecyl maleate as a colorless transparent solid.

3-2 Synthesis of Monododecyl Chloride Maleate To 116 g (0.558 mol) of phosphorus pentachloride and 40 mL of chloroform, 158.8 monododecyl maleate was added.
What melt | dissolved g (0.558 mol) in chloroform 40mL was dripped slowly, keeping below 30 degreeC. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then 60
The mixture was heated to ℃, decompressed with an aspirator, the generated phosphorus oxychloride and chloroform were distilled off, and 155.8 g of the brown oily compound maleic acid monododesyl chloride.
(Yield 92%) was obtained.

3-3 Monododecyl Maleate Mono 3,3,4,5,5,6,6,6-Synthesis of Nonafluorohexyl 3,3,4,4,5,5,6,6 164.64 g (0.623 mol) of 6-nonafluorohexanol and 49.27 g (0.623 mol) of pyridine were dissolved in 280 mL of chloroform and cooled in an ice bath, while maintaining the internal temperature at 20 ° C. or lower, dodecyl chloride maleate 1
55.78 g (0.566 mol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, 1000 mL of chloroform was added, the organic phase was washed with a 1 mol / L hydrochloric acid aqueous solution, the organic layer was recovered, and the organic solvent was distilled off under reduced pressure.
Purification operation was performed by silica gel column chromatography (hexane / chloroform: 10/0 to 5/5 (volume ratio)) to obtain 48.2 g of a colorless transparent oily target compound.
(Yield 18%) was obtained.

3-4 Sodium monododecyl mono 3,
Synthesis of 3,4,4,5,5,6,6,6-nonafluorohexyl sulfosuccinate (FS-12) Maleic acid monododecyl mono 3,4,4,5,5,5
4,6,6-Nonafluorohexyl 48.0 g (9
0.0mmol), sodium bisulfite 10.4g
(99.0 mmol), water-ethanol (volume ratio 1 /
1) 50 mL was added and the mixture was heated under reflux for 5 hours. Then, 1000 mL of ethyl acetate was added, the organic phase was washed with a saturated sodium chloride aqueous solution, the organic phase was recovered, and the organic solvent was distilled off under reduced pressure to obtain a colorless transparent compound (FS-12).
5 g (yield 22%) was obtained.

Melting point and ¹ H-NMR of the obtained compound
The data are as follows. Melting point: 258 to 260 ° C. ¹ H-NMR (DMSO-d ₆ ): δ 0.85 (t, 3
H), 1.23 (br, 18H), 1.51 (br, 2)
H), 2.49-2.51 (m, 2H), 2.80-
2.96 (m, 2H), 3.60-3.68 (m, 1
H), 3.95 (br, 2H), 4.28 (t, 2)
H).

(Synthesis Example 4 Synthesis of Exemplified Compound FS-20) 4-1 Maleic Acid Mono-2-ethylhexyl Mono 3,
Synthesis of 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 3,3,4,4,5,5,6,6,7,7, 8, 8, 8
-142 g of tridecafluorooctanol (0.39
and triethylamine 59.7 mL (0.
(43 mol) was dissolved in 200 mL of chloroform, cooled in an ice bath, and 106 g (0.43) of maleic acid (2-ethylhexyl) chloride while maintaining the internal temperature at 20 ° C or lower.
(mol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 2 hours. Then add 1000 mL of chloroform and 1 mol
/ L hydrochloric acid water and a saturated sodium chloride aqueous solution, after washing the organic phase, the organic phase is recovered, the organic solvent is distilled off under reduced pressure,
Purification was performed by silica gel column chromatography (hexane / chloroform: 10/0 to 6/4 (volume ratio)) to obtain 90 g of the desired product as a colorless transparent oily compound.
(Yield 37%) was obtained.

4-2 Sodium mono 2-ethylhexyl mono 3,3,4,5,5,6,6,7,7,
Synthesis of 8,8,8-tridecafluorooctyl sulfosuccinate (FS-20) Maleic acid mono 2-ethylhexyl mono 3,3,4
4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 90.0 g (0.157 mol), sodium bisulfite 17.9 g (0.172 mol),
Add 90 mL of water-ethanol (1/1 (volume ratio)) and add 1
The mixture was heated under reflux for 0 hours. Then add chloroform to 1000 m
L was added and the organic phase was washed with a saturated aqueous solution of sodium chloride, the organic phase was recovered, the organic solvent was distilled off under reduced pressure, and recrystallization operation was carried out with 300 mL of toluene. 50.0 g (yield 47%) of the target compound (FS-20) was obtained as crystals.

Melting point and ¹ H-NMR of the obtained compound
The data are as follows. Melting point: 244-246 ° C. ¹ H-NMR (DMSO-d ₆ ): δ 0.85 (t, 3
H), 1.23 (br, 18H), 1.51 (br, 2)
H), 2.49-2.51 (m, 2H), 2.80-
2.96 (m, 2H), 3.60-3.68 (m, 1
H), 3.95 (br, 2H), 4.28 (t, 2)
H).

Synthesis Example 5 Synthesis of Exemplified Compound FR-1 5-1 Di (3,3,4,4,5,5, maleic acid)
Synthesis of 6,6,6-nonafluorohexyl) Maleic anhydride 9.8 g (0.10 mol), 3,3,3
52.8 g (0.20 mol) of 4,4,5,5,6,6,6-nonafluorohexanol and 0.5 g of p-toluenesulfonic acid monohydrate in 30 mL of toluene were distilled off to form water. While heating and refluxing for 24 hours. Then, cool to room temperature, add hexane and ethyl acetate, and add 1 mol / L.
The organic phase was washed with an aqueous solution of sodium hydroxide and a saturated aqueous solution of sodium chloride, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure, followed by silica gel column chromatography (hexane / ethyl acetate: 9 / 1-8 / 2 v
/ V) to perform the purification operation to obtain 5
3.2 g (yield 88%) was obtained.

5-2 Synthesis of FR-1 Maleic acid di (3,3,4,4,5,5,6,6,6)
-Nonafluorohexyl) 42.8 g (69 mmol), sodium bisulfite 7.9 g (76 mmol), and water-ethanol (1/1 v / v) 50 mL were added, and the mixture was heated under reflux for 3 hours and cooled to 0 ° C. Then, the precipitated solid was collected by filtration, and recrystallized with acetonitrile, and the obtained crystal was dried under reduced pressure at 60 ° C. to obtain 27.0 g (yield 54%) of the target compound as a white crystal. .

The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ) δ2.49-2.62
(M, 4H), 2.85-2.99 (m, 2H), 3.
68 (dd, 1H), 4.23-4.35 (m, 4
H).

(Synthesis Example 6 Synthesis of Exemplified Compound FR-2) 6-1 Di (3,3,4,4,5,5, maleic acid)
Synthesis of 6,6,7,7,8,8,8-tridecafluorooctyl) 4.61 g (47 mmol) of maleic anhydride, 3,3,3
4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl alcohol 34.1 g (98 mmol), p-toluenesulfonic acid monohydrate 0.24 g, and toluene 140 mL. The resulting mixture was heated under reflux for 10 hours while distilling off the produced water. Then, the mixture was cooled to room temperature, ethyl acetate was added, the organic phase was washed with a saturated sodium chloride aqueous solution, and the organic phase was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure, followed by silica gel column chromatography (hexane / acetic acid). Ethyl: 8/2 v / v) was used for purification, and 19.7 g (yield 52%) of the desired product as a white solid.
Obtained.

6-2 Synthesis of FR-2 Maleic acid di (3,3,4,4,5,5,6,6,6)
7,7,8,8,8-tridecafluorooctyl) 1
0.0 g (12.4 mmol), sodium bisulfite 1.55 g (14.9 mmol), water-ethanol (1
(1 v / v) 15 mL, and the mixture was heated under reflux for 7 hours, cooled to room temperature, and the obtained crystals were dried under reduced pressure at 60 ° C. to give 9.38 g of the target compound as white crystals (yield 8
1%) was obtained.

¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ) δ 2.48 (m, 4
H), 2.97 (m, 2H), 3.82 (m, 1H),
4.18-4.58 (m, 4H).

(Synthesis Example 7 Synthesis of Exemplified Compound FR-4) 7-1 Maleic acid di (4,4,5,5,6,6,6)
Synthesis of 7,7,7-nonafluoroheptyl) Maleic anhydride 17.6 g (0.18 mol), 4,4
100 g of 5,5,6,6,7,7,7-nonafluoroheptanol (0.36 mol) and 0.5 g of p-toluenesulfonic acid monohydrate in 250 mL of toluene were distilled off to form water. While heating and refluxing for 12 hours. Then, the mixture was cooled to room temperature, chloroform was added, and the organic phase was washed with a 1 mol / L sodium hydroxide aqueous solution and a saturated sodium chloride aqueous solution to quantitatively obtain 114.1 g of the desired product as a white solid.

7-2 Synthesis of FR-4 Maleic acid di (4,4,5,5,6,6,7,7,7
-Nonafluoroheptyl) 95.8 g (156 mmol), sodium bisulfite 7.9 g (172 mmol) and water-ethanol (1/1 v / v) 100 mL were added, and the mixture was heated under reflux for 20 hours, and then ethyl acetate was added. Then
The organic phase was washed with a saturated aqueous sodium chloride solution, the organic layer was dried over sodium sulfate, and the solvent was concentrated under reduced pressure.
Recrystallize the aceto with tolyl to obtain 60 crystals.
After drying under reduced pressure at 0 ° C., 95.
8 g (yield 83%) was obtained.

¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ) δ 1.80 (m, 4
H), 2.19-2.34 (m, 4H), 2.79-.
2.97 (m, 2H), 3.68 (dd, 1H), 4.
01-4.29 (m, 4H).

(Synthesis Example 8 Synthesis of Exemplified Compound FR-19) 8-1 Itaconic acid di (3,3,4,4,5,5,5)
Synthesis of 6,6,6-nonafluorohexyl) 13.5 g (0.12 mol) of itaconic anhydride, 3,3,3
Toluene 500 4,4,5,5,6,6,6-nonafluorohexanol 69.8 g (0.26 mol), p-toluenesulfonic acid monohydrate 1.14 g (6 mmol)
The mixture was heated under reflux for 12 hours while distilling off the produced water in mL. Then cool to room temperature, add ethyl acetate, add 1
The organic phase was washed with a mol / L sodium hydroxide aqueous solution and a saturated sodium chloride aqueous solution to obtain 51.3 g (69%) of the desired product as an oily compound.

8-2 Synthesis of FR-19 Itaconic acid di (3,3,4,5,5,6,6,6)
-Nonafluorohexyl) 20.0 g (32 mmol), sodium bisulfite 4.0 g (38 mmol), and water-ethanol (1/1 v / v) 25 mL were added, and the mixture was heated under reflux for 6 hours, and then ethyl acetate was added. The organic phase was washed with a saturated aqueous solution of sodium chloride, the organic layer was dried over sodium sulfate, the solvent was concentrated under reduced pressure, and then recrystallized with acetonitrile.
After drying for 2 hours under reduced pressure, the target compound is obtained as white crystals.
0.6 g (yield 89%) was obtained.

¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ) δ2.49-2.78
(M, 5H), 3.04-3.13 (m, 2H), 3.
47 (br, 2H) 4.23 (t, 4H).

Synthesis Example 9 Synthesis of Exemplified Compound FT-1 9-1 2- (N, N-dimethylaminoethanethionyl) maleic acid 1,4-di (3,3,4,4,5,5)
Synthesis of 5,6,6,6-nonafluorohexyl) Maleic acid 1,4-di (3,3,4,4,5,5,5)
25.1 g (4,6,6,6-nonafluorohexyl)
1 mmol), 6.4 g (45 mmol) of N, N-dimethylaminoethanethiol hydrochloride, and 5.7 g (41 mmol) of potassium carbonate were dissolved in 60 mL of N, N dimethylformamide, and the mixture was heated at 60 ° C. for 4 hours. It was stirred. Then, after adding 500 mL of chloroform and washing the organic phase with a saturated aqueous solution of sodium hydrogencarbonate, the organic layer is recovered, the organic solvent is distilled off under reduced pressure, and silica gel column chromatography (hexane / ethyl acetate: 8/2 to 0). / 10
(Volume ratio)) to carry out the purification operation to obtain the target compound at 15.8.
g (yield 54%) was obtained.

9-2 Synthesis of FT-1 2- (N, N-dimethylaminoethanethionyl) maleic acid 1,4-di (3,3,4,4,5,5,6,6,6)
5.8 g (22 mmol) of 6-nonafluorohexyl), 1.5 mL (24 mmol) of iodomethane and 60 mL of methanol were added, and the mixture was heated under reflux for 10 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, and a recrystallization operation was performed with hexane-ethyl acetate (2/1 (volume ratio)) to obtain 18.9 g of the target compound (FS-1) as a colorless transparent solid ( Yield 100%).

The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ): δ2.66 (m, 4)
H), 2.85-2.92 (m, 2H), 3.09
(M, 11H), 3.54 (d, 2H), 3.86-
3.91 (m, 1H), 4.31-4.47 (m, 4
H).

Synthesis Example 10 Synthesis of Exemplified Compound FT-47 Maleic acid 1-mono (2-ethylhexyl) 4-
20.0 g (42 mmol) of mono (3,3,4,4,5,5,6,6,6-nonafluorohexyl), N, N
-4.0 g (46 mmol) of dimethylaminoethylamine and 5.8 g (42 mmol) of potassium carbonate were added as N,
It was dissolved in 60 mL of N dimethylformamide and stirred at 60 ° C. for 12 hours. After that, add 500 mL of chloroform
In addition, after washing the organic phase with a saturated aqueous solution of sodium hydrogencarbonate, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol: 98/2 (volume ratio)). This was performed to obtain 15.9 g of an oily compound (yield 67%). Then, 60 mL of methanol and 1.9 mL (31 mmol) of iodomethane were added, and the mixture was heated under reflux for 8 hours. After that, the organic solvent was distilled off under reduced pressure with an evaporator to obtain 19.9 g (yield 67%) of a target compound (FS-47) as a yellow wax-like compound.

The data of ¹ H-NMR of the obtained compound is as follows. ¹ H-NMR (DMSO-d ₆ ): δ 0.83 (m, 6)
H), 1.20 (m, 8H), 1.53 (m, 1H),
2.61-2.97 (m, 6H), 2.90 (br, 1
H), 3.09 (s, 9H), 3.17 (s, 1H),
3.30 (m, 2H) 3.66 (m, 1H), 4.02
(M, 2H), 4.35 (t, 2H).

Synthesis Example 11 Synthesis of Exemplified Compound FS-64 Maleic acid 1-mono (2-ethylhexyl) 4-
35.5 g (75 mmol) of mono (3,3,4,4,5,5,6,6,6-nonafluorohexyl), N, N
11.7 g of dimethylaminoethanethiol hydrochloride
(82 mmol) and 10.4 g (75 mmol) of potassium carbonate were dissolved in 60 mL of N, N dimethylformamide, and the mixture was stirred at 60 ° C. for 4 hours. Then, 500 mL of chloroform was added, the organic phase was washed with a saturated aqueous solution of sodium hydrogen carbonate, the organic layer was recovered, and the organic solvent was distilled off under reduced pressure. Then, 100 mL of methanol and 4.7 mL (75 mmol) of iodomethane were added, and the mixture was heated under reflux for 8 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, and recrystallization operation was performed with hexane-ethyl acetate (2/1 (volume ratio)) to obtain 49.7 g of the target compound as a yellow wax-like compound (yield 92%). )Obtained.

The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ): δ 0.83 (m, 6)
H), 1.29 (m, 8H), 1.52 (m, 1H),
2.64 (m, 2H), 2.84-2.91 (m, 2
H), 3.09 (s, 9H), 3.16 (d, 2H)
3.56 (m, 2H), 3.85 (dd, 1H), 4.
01 (m, 2H), 4.36 (br, 2H).

The silver halide emulsion used in the present invention is
Silver bromide, silver chloride, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodobromide and the like are preferable. The morphology of the silver halide grains may be normal crystals such as octahedron, cubic and tetradecahedral, but tabular grains are more preferred.

Opposite (1
11) Particles composed of a main surface and side surfaces connecting the main surfaces can be mentioned. The tabular grain emulsion comprises silver iodobromide or silver chloroiodobromide. Although it may contain silver chloride, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. The silver iodide content is 4
It is 0 mol% or less, preferably 20 mol% or less. Regardless of the silver iodide content, the variation coefficient of the distribution of silver iodide content between grains is preferably 20% or less, and particularly preferably 10% or less.

The silver iodide distribution preferably has a structure within the grain. In this case, the structure of silver iodide distribution is 2
There may be a triple structure, a triple structure, a quadruple structure and even more structures. Further, the silver iodide content may be continuously changed inside the grain.

50% or more of the total projected area has an aspect ratio of 2
It is occupied by the above particles. Here, the projected area and aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method in which a shadow is cast together with a latex sphere for reference. When viewed from above, tabular grains usually have a hexagonal, triangular or circular shape, and the aspect ratio is the value obtained by dividing the diameter of a circle having an area equal to the projected area by the thickness. The tabular grain shape is preferably such that the ratio of hexagons is higher, and the ratio of the lengths of adjacent sides of the hexagons is preferably 1: 2 or less. The tabular grains have a projected area diameter (also referred to as "circle equivalent diameter") of 0.1.
The thickness is preferably μm or more and 20.0 μm or less, more preferably 0.2 μm or more and 10.0 μm or less. What is the projected area diameter?
It is the diameter of a circle having an area equal to the projected area of silver halide grains. The thickness of the tabular grains is 0.01 μm or more and 0.1 μm or more.
It is 5 μm or less, preferably 0.02 μm or more and 0.4 μm or less. The thickness of a tabular grain is the distance between two principal planes. The equivalent-sphere diameter is preferably 0.1 μm or more and 5.0 μm or less, and more preferably 0.2 μm or more and 3 μm or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to that of individual particles. Also, the aspect ratio is 1 or more and 1
00 or less is preferable, and 2 or more and 50 or less is more preferable. The aspect ratio is a value obtained by dividing the projected area diameter of a grain by the thickness of the grain.

The silver halide grains used in the present invention are preferably monodisperse. The variation coefficient of the spherical equivalent diameter of all silver halide grains of the present invention is 30% or less, preferably 2
It is 5% or less. Further, in the case of tabular grains, the coefficient of variation of projected area diameter is also important, and the coefficient of variation of projected area diameter of all silver halide grains of the present invention is preferably 30% or less, more preferably 25% or less. And more preferably 20% or less. The variation coefficient of the thickness of the tabular grains is preferably 30% or less, more preferably 25% or less, still more preferably 20% or less. The coefficient of variation is the value obtained by dividing the standard deviation of the distribution of the equivalent diameter of individual silver halide grains by the average equivalent diameter, or the standard deviation of the distribution of the thickness of individual tabular silver halide grains divided by the average thickness. It is a value.

The twin plane spacing of the tabular grains used in the present invention is 0.012 μm or less as described in US Pat. No. 5,219,720, and JP-A-5-249585.
The (111) principal plane distance / twin plane distance may be 15 or more as described in No. 1, and may be selected according to the purpose.

Since the higher the aspect ratio is, the more remarkable the effect is obtained, 50% or more of the total projected area of the tabular grain emulsion is preferably occupied by grains having an aspect ratio of 5 or more. More preferably, the aspect ratio is 8 or more. If the aspect ratio becomes too large, the coefficient of variation of the particle size distribution described above tends to increase, so the aspect ratio is usually preferably 50 or less.

The dislocation lines of tabular grains are described, for example, in J. F. H
amilton, Photo. Sci. Eng. , 11,
57, (1967) and T.W. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to generate dislocation lines from the emulsion, put them on a mesh for electron microscope observation, and to prevent damage (printout, etc.) due to electron beams In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the grain obtained by such a method, the position and number of dislocation lines for each grain when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more on average per grain. More preferably 20 on average per particle
More than a book. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 lines, and it is possible to clearly distinguish from the case where there are only a few lines. The average number of dislocation lines per grain is calculated as the number average by counting the number of dislocation lines for 100 grains or more.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer circumference, and dislocation lines are generated starting from the position of x% of the length of the distance from the center of the tabular grain to the side (outer circumference) and reaching the outer circumference. 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 start positions of the dislocation lines is similar to the particle shape, but it is not a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The dislocation lines are crystallographically in the (211) direction, but they are often meandering and may intersect with each other.

Further, the dislocation lines may be substantially uniform over the entire outer circumference of the tabular grain, or may be locally located on the outer circumference. That is, taking hexagonal tabular silver halide grains as an example, the dislocation lines may be limited only in the vicinity of the six vertices, or the dislocation lines may be limited in the vicinity of only one of the vertices. On the contrary, it is 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 centers of two parallel main planes of the tabular grain.
When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, they are randomly formed, and the length of each dislocation line is also random. In some cases, they are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are often straight or meandering. Also, they often intersect with each other.

The positions of the dislocation lines may be limited to the outer circumference, the main plane, or the local positions as described above, or may be formed by combining these.
That is, they may exist on the outer circumference and the main plane at the same time.

The silver iodide content on the grain surface of this tabular grain emulsion is preferably 10 mol% or less, particularly preferably 5 mol% or less. The silver iodide content on the grain surface of the present invention is measured using XPS. Regarding the principle of the XPS method used to analyze the content of silver iodide near the surface of silver halide grains, refer to "Electron Spectroscopy" by Aihara et al. (Kyoritsu Library-16, Kyoritsu Publishing, 1978). can do. The standard measurement method of XPS is to use Mg-Kα as an excitation X-ray, and to produce iodine (I) and silver (Ag) photoelectrons (usually I-3d5) emitted from silver halide in an appropriate sample form. / 2, Ag-3d5 / 2). In order to determine the iodine content, iodine (I) was used by using several kinds of standard samples with known iodine contents.
And silver (Ag) photoelectron intensity ratio (strength (I) / strength (A
It is possible to obtain a calibration curve of g)) and obtain it from this calibration curve. In the case of silver halide emulsion, XPS must be measured after gelatin adsorbed on the surface of silver halide grains is decomposed and removed by a protease or the like. A tabular grain emulsion having a silver iodide content of 10 mol% or less on the grain surface refers to an emulsion grain contained in one emulsion having a silver iodide content of 10 mol% or less when analyzed by XPS. . In this case, when two or more kinds of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as a centrifugation method or a filtration method and then analyze the emulsions of the same kind.

The structure of the tabular grain emulsion used in the present invention is preferably, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide and a higher-order structure having a higher structure. The boundary of the silver iodide content between the structures may be clear or may have a continuous and gradual change. Usually, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks having different silver iodide contents, and the tail is drawn toward the high silver iodide content. Such an X-ray diffraction profile is shown.

The silver iodide content of the layer inside the surface is preferably higher than the silver iodide content of the surface, and the silver iodide content of the layer inside the surface is preferably 3 mol% or more. More preferably, it is 5 mol% or more.

Further, in the tabular grains used in the present invention, the parallel principal planes are (111) planes, and the length of the side having the maximum length is smaller than that of the side having the minimum length. The hexagonal silver halide grains having a ratio of 2 or less may be grains having at least one epitaxial junction per grain at the apex and / or the side face and / or the main plane portion. Epitaxially joined grains are grains having a crystal part (that is, an epitaxial part) joined to the grain in addition to the silver halide grain body, and the joined crystal part usually protrudes from the silver halide grain body.
The ratio of the joined crystal part (epitaxial part) to the total silver amount of the grains is preferably 2% or more and 30% or less, and 5% or more 1
It is more preferably 5% or less. The epitaxial part may be present in any part of the particle body, but is preferably the particle main surface part, the particle edge part, or the particle corner part. The number of epitaxial layers is preferably at least one. The composition of the epitaxial portion is AgCl, AgBrCl, AgB.
rClI, AgBrI, AgI, AgSCN and the like are preferable. When the epitaxial portion is present, dislocation lines may be present inside the grains, but they may not be present.

Next, a method for preparing tabular grains used in the present invention will be described. As the preparation process of the present invention,
(A) Base particle forming step and subsequent particle forming step ((b) step). Basically, it is more preferable to carry out the step (b) after the step (a), but only the step (a) may be carried out. The step (b) includes (b1) dislocation introduction step, (b2) corner dislocation limited introduction step, or (b)
3) Any of the epitaxial bonding steps may be used, and at least one may be combined, or two or more may be combined.

First, (a) base particle forming step will be described. The base portion is preferably at least 50% or more of the total amount of silver used for grain formation, and more preferably 6%.
It is 0% or more. The average content of iodine with respect to the amount of silver in the base portion is preferably 0 mol% or more and 30% mol or less, and more preferably 0 mol% or more and 15 mol% or less. Further, the base portion may have a core-shell structure if necessary. At this time, the core portion of the base portion is preferably 50% or more and 70% or less with respect to the total silver amount of the base portion, and the average iodine composition of the core portion is preferably 0 mol% or more and 30 mol% or less, or 0 mol% or more and 15 mol% or less. % Or less is more preferable. The iodine composition of the shell is 0 mol% or more and 3 mo
It is preferably 1% or less.

The silver halide emulsion is generally prepared by forming silver halide nuclei and then growing silver halide grains to obtain grains of a desired size. The present invention is also the same. There is no difference in being there. The formation of tabular grains includes at least the steps of nucleation, ripening and growth. This process is described in U.S. Pat.
It is described in detail in No. 7. Below, nucleation, aging,
The growth and each step will be described.

1. Nucleation step The nucleation of tabular grains is generally carried out by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding a protective colloid aqueous solution, or a protective colloid solution containing an alkali halide. A single jet method in which a silver salt aqueous solution is added to is used. Also,
A method of adding an alkali halide aqueous solution to a protective colloid solution containing a silver salt can also be used if necessary.
Furthermore, if necessary, a protective colloid solution, a silver salt solution and an aqueous solution of an alkali halide are added to the mixer disclosed in JP-A-2-44335 and immediately transferred to a reaction vessel to form a tabular grain core. It can also be formed. Further, as disclosed in US Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto. .

Although gelatin is used as the protective colloid, natural polymers and synthetic polymers other than gelatin are also used. The types of gelatin include alkali-processed gelatin and oxidation-processed gelatin in which the methionine group in the gelatin molecule is oxidized with hydrogen peroxide (methionine content 40 μm).
mol / g or less), amino group-modified gelatin of the present invention (for example, phthalated gelatin, trimellitated gelatin, succinated gelatin, maleated gelatin, esterified gelatin), and low molecular weight gelatin (molecular weight: 3000 to 300).
40,000) is used. Regarding the oxidation-processed gelatin, Japanese Patent Publication No. 5-12696, and regarding amino group-modified gelatin, JP-A Nos. 8-82883 and 11-143002.
You can refer to the description of the issue. In addition, if necessary, JP-A-1
In the molecular weight distribution measured by the Paggy method described in 1-237704, lime-processed bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more may be used. Further, for example, the starch described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymer is Japanese Patent Publication 7-11
No. 1550, Research Disclosure No. 176
Volume 17643 (December 1978), Section IX.

Excess halogen salt in nucleation is Cl
^- , Br ⁻ , and I ⁻ are preferable, and these may be present alone or in plural. Total halogen salt concentration is 3
It is not less than × 10 ^-5 mol / L and not more than 0.1 mol / L, preferably not less than 3 × 10 ^-4 mol / L and not more than 0.01 mol / L.

The halogen composition in the halide solution added at the time of nucleation is preferably Br ⁻ , Cl ⁻ , and I ⁻ , and these may be present alone or in plural. JP-A-1
May be used nucleation such that 10 mole% or more relative to the amount of silver is chlorine content as described was used in the nucleation No. 0-293372, this time Cl ^- concentrations of total 10 mol% or more for halogen salt concentration 1
00 mol% or less is preferable, 20 mol% or more and 80 m
It is more preferably ol% or less.

The protective colloid may be dissolved in a halide solution added at the time of nucleation, or the gelatin solution may be added simultaneously at the time of nucleation, separately from the halide solution.

The temperature during nucleation is preferably 5 to 60 ° C., but more preferably 5 to 48 ° C. in the case of producing fine grain tabular grains having an average grain size of 0.5 μm or less. The pH of the dispersion medium is preferably 4 or more and 8 or less when using amino group-modified gelatin, but is 2 or more and 8 when using other gelatin.
The following are preferred.

2. Aging process 1. In the nucleation in (1), fine particles other than tabular grains (especially octahedral and single twinned grains) are formed. Before starting the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape which should be tabular grains and good monodispersity. To make this possible, it is well known to perform nucleation followed by Ostwald ripening.

Immediately after the nucleation, the pBr is adjusted, and then the temperature is raised and ripening is carried out until the ratio of hexagonal tabular grains becomes maximum. At this time, a protective colloid solution may be additionally added.
The concentration of protective colloid in the dispersion medium solution at that time is 1
It is preferably 0% by mass or less. The additional protective colloid used at this time is the above-mentioned alkali-processed gelatin,
The amino group-modified gelatin, oxidized gelatin, low molecular weight gelatin, natural polymer, or synthetic polymer of the present invention can be used. In addition, if necessary, JP-A-11-237704
In the molecular weight distribution measured by the Paggy method described in No. 6, a lime-processed bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more may be used. Also, for example, European Patent No. 758758 and US Patent No. 5,
The starch described in No. 733,718 may be used.

The aging temperature is 40 to 80 ° C., preferably 50 to 80 ° C., and pBr is 1.2 to 3.0.
The pH is 4 if amino group-modified gelatin is present.
It is preferably 8 or more and 8 or less, but 2 or more and 8 or less in the case of other gelatins.

At this time, a silver halide solvent may be added in order to rapidly eliminate grains other than the tabular grains. In this case, the concentration of the silver halide solvent is
It is preferably 0.3 mol / L or less, more preferably 0.2 mol / L or less. Aged in this way, almost 100%
Only tabular grains are used.

After the ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows. In the case of an alkaline silver halide solvent such as NH ₃ , it is nullified by adding an acid having a large solubility product with Ag ⁺ such as HNO ₃ . In the case of a thioether type silver halide solvent, it is made ineffective by adding an oxidizing agent such as H ₂ O ₂ as described in JP-A-60-136736.

In the method for producing an emulsion of the present invention, the end of the ripening step means a tabular grain whose main plane is a hexagon or a triangle and which has at least two twin planes (regular and regular). The point at which the single twin grains) disappear. The disappearance of grains other than those having tabular grains whose main planes are hexagonal or triangular and having at least two twin planes can be confirmed by observing a TEM image of a replica of the grains.

In the aging step, if necessary, JP-A-1
You may provide the over-ripening process of 1-174606.
The overripening step is a step of erasing tabular grains having a slow anisotropic growth speed by aging (ripening step) until the ratio of hexagonal tabular grains becomes maximum, and further aging the tabular grains themselves by Ostwald ripening. . When the number of tabular grains obtained in the aging step is 100, it is preferable to reduce the number of tabular grains to 90 or less by the over-aging step.
Further, it is more preferable to reduce it to 60 or more and 80 or less.

In the emulsion manufacturing method of the present invention, the conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. Further, in the overripening step, a silver halide solvent can be added in the same manner as in the ripening step, and its kind, concentration and the like can be set to the same as those in the ripening step.

3. It is preferable to keep pBr at 1.4 to 3.5 during the crystal growth period following the ripening process. When the concentration of the protective colloid in the dispersion medium solution before entering the growth step is low (1% by mass or less), the protective colloid may be additionally added. In addition, protective colloid may be added during the growth process. The time of additional addition may be any time during the growth process. The protective colloid concentration in the dispersion medium solution is preferably 1 to 10% by mass. As the protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin of the present invention, oxidation-treated gelatin, natural polymer, or synthetic polymer is used. If necessary, lime-processed bone gelatin containing 30% or more of components having a molecular weight of 280,000 or more in the molecular weight distribution measured by the Paggy method described in JP-A No. 11-237704 may be used. Also, for example, European Patent No. 758758 and US Patent No. 5,73.
You may use the starch described in 3,718. The pH during growth is 4 if amino group-modified gelatin is present.
-8 or less are preferable, and other than that, 2-8 are preferable. The addition rate of Ag ⁺ and halogen ions during the crystal growth period is preferably set to 20 to 100%, preferably 30 to 100% of the crystal growth rate. In this case, the rate of addition of silver ions and halogen ions is increased along with the crystal growth. In that case, as described in JP-B-48-36890 and 52-16364, the addition rate of silver salt and halogen salt aqueous solution is added. May be increased or the concentration of the aqueous solution may be increased.

When the double jet method in which an aqueous solution of silver salt and an aqueous solution of halogen salt are added at the same time, in order to prevent the introduction of growth dislocation due to non-uniformity of iodine, improve the stirring of the reaction vessel and dilute the concentration of the added solution. Preferably.

A method in which the AgI fine grain emulsion prepared outside the reaction vessel is added simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution is more preferable. At this time, the growth temperature is preferably 50 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. Further, the AgI fine grain emulsion to be added may be prepared in advance, or may be added while being continuously prepared. The preparation method at this time is described in JP-A-10-4357.
You can refer to No. 0.

The average grain size of the added AgI emulsion is 0.
It is from 0.1 μm to 0.1 μm, preferably from 0.02 μm to 0.08 μm. The iodine composition of the base particles is
It can be changed depending on the amount of the AgI emulsion to be added.

Further, silver iodobromide fine particles may be added instead of the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, the amount of iodine in the fine particles is made equal to the amount of iodine in the desired base particles, whereby base particles having a desired iodine composition can be obtained. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while continuously preparing them. The added silver iodobromide fine particle size is 0.005μ
It is m or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less. Temperature during growth is 60 ° C or higher 9
It is 0 ° C. or lower, preferably 70 ° C. or higher and 85 ° C. or lower. Furthermore, the ion addition method, the AgI fine particle addition method, and the AgBrI fine particle addition method may be combined.

In the present invention, tabular grains preferably have dislocation lines, but it is preferable that dislocation lines do not exist in the base portion in order to reduce pressure desensitization. The dislocation lines of tabular grains are
For example, JF Hamilton, Phot. Sci. Eng., 11,57 (196
7), T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to generate dislocation lines from the emulsion, put them on a mesh for electron microscope observation, and to prevent damage (printout, etc.) due to electron beams In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the grain obtained by such a method, the position and number of dislocation lines for each grain when viewed from the direction perpendicular to the main plane can be obtained.

Next, the step (b) will be described. First, the step (b1) will be described. The step (b1) comprises a first shell step and a second shell step. The first shell is provided on the base described above. The ratio of the first shell is preferably 1% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 20% by mole or more and 100% by mole or less.
More preferably, the ratio of the first shell is 1% with respect to the total silver amount.
The average silver iodide content is 25 mol% or more and 100 mol% or less. To grow the first shell on the substrate, basically, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide and bromide are added by the double jet method. Alternatively, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide are added by the double jet method. Alternatively, an aqueous halogen solution containing iodide is added by the single jet method.

Any of the above methods or a combination thereof may be used. As is clear from the average silver iodide content of the first shell, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal when the first shell is formed. In either case, usually, silver iodide disappears and all the silver iodobromide mixed crystals are converted during the subsequent formation of the second shell.

As a preferable method for forming the first shell, there is a method of adding silver iodobromide or silver iodide fine grain emulsion and ripening and dissolving. Further, as a preferable method, there is a method of adding a silver iodide fine grain emulsion and then adding an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halogen solution. In this case, the dissolution of the silver iodide fine grain emulsion is promoted by the addition of an aqueous silver nitrate solution.
Mol%. Then, the added silver nitrate aqueous solution is calculated as the second shell. The silver iodide fine grain emulsion is preferably added rapidly.

The rapid addition of a silver iodide fine grain emulsion means that
It is preferable to add the silver iodide fine grain emulsion within 10 minutes. More preferably, it means addition within 7 minutes. These conditions may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent, type and concentration, but as described above, shorter conditions are preferable. It is preferable that substantially no aqueous silver salt solution such as silver nitrate is added at the time of addition.
The temperature of the system during addition is preferably 40 ° C or higher and 90 ° C or lower,
It is particularly preferably 50 ° C. or higher and 80 ° C. or lower.

The silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. In its crystal structure, silver iodide has β-form and γ-form.
There may be α-forms or α-form-like structures as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited,
A mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion is described in US Pat. No. 5,004,679.
It may be formed immediately before the addition described in No.
Although it may be one that has been subjected to a normal water washing step, in the present invention, one that has been subjected to a normal water washing step is preferably used. A silver iodide fine grain emulsion is described in US Pat.
It can be easily formed by the method described in No. 2,026. A double jet addition method of an aqueous silver salt solution and an aqueous iodide salt solution, which carries out grain formation with a constant pI value during grain formation, is preferred. Here, pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. The temperature, pI, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent, type and concentration are not particularly limited, but the grain size is 0.1 μm or less, more preferably 0.07 μm. The following are convenient for the present invention.
The shape of the particles cannot be completely specified because they are fine particles, but the variation coefficient of the particle size distribution is preferably 25% or less.
Especially when it is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing the silver iodide fine grains on a mesh for electron microscope observation and directly observing by a transmission method instead of the carbon replica method. This is because the particle size is small and the measurement error is large in the observation by the carbon replica method. Grain size is defined as the diameter of a circle with a projected area equal to the observed grain. The particle size distribution is also calculated using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of 0.0
It is 6 μm or less and 0.02 μm or more, and the variation coefficient of the particle size distribution is 18% or less.

After forming the above-mentioned grains, the silver iodide fine grain emulsion is preferably washed with water and adjusted in the usual manner as described in US Pat. The silver halide concentration is adjusted. The pH is preferably 5 or more and 7 or less. The pI value is a pI value at which the solubility of silver iodide is the lowest or a pI value higher than that value.
It is preferable to set the I value. As the protective colloid agent, normal gelatin having an average molecular weight of about 100,000 is preferably used. A low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. Further, it may be convenient to mix and use the above gelatins having different molecular weights. Emulsion 1k
The amount of gelatin per gram is preferably 10 g or more and 100 g
It is the following. It is more preferably 20 g or more and 80 g or less. The amount of silver in terms of silver atoms per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably 20 g
It is above 80 g. The amount of gelatin and / or the amount of silver is preferably selected to a value suitable for rapidly adding the silver iodide fine grain emulsion.

The silver iodide fine grain emulsion is usually dissolved in advance and added, but it is necessary to sufficiently enhance the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective in preventing the generation of bubbles during stirring. Specifically, US Pat. No. 5,
The defoaming agent described in Examples of 275,929 is used.

As a more preferable method of forming the first shell, US Pat. No. 5,496,6 is used instead of the conventional iodide ion supply method (method of adding free iodide ion).
Using the iodide ion-releasing agent described in No. 94, a silver halide phase containing silver iodide can be formed while rapidly generating iodide ions.

The iodide ion-releasing agent releases an iodide ion by a reaction with an iodide ion-releasing regulator (base and / or nucleophile). The nucleophile used at this time is preferably one of the following chemicals: Seed. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, Examples thereof include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines and sulfides.

The release rate and timing of iodide ions can be controlled by controlling the concentrations of bases and nucleophiles, the method of addition, and the temperature of the reaction solution. The base is preferably alkali hydroxide.

The preferred concentration range of the iodide ion-releasing agent and the iodide ion-releasing regulator used for rapidly generating iodide ions is 1 × 10 ^{-7 to} 20 M, more preferably 1 × 10 ^-5 〜. 10M, more preferably 1 × 1
It is 0 ^{-4 to 5} M, particularly preferably 1 x 10 ^{-3 to 2} M.
If the concentration exceeds 20 M, the iodide ion-releasing agent having a large molecular weight and the added amount of the iodide ion-releasing agent become too large with respect to the capacity of the grain forming container, which is not preferable. On the other hand, if it is less than 1 × 10 ⁻⁷ M, the reaction rate of iodide ion-releasing becomes slow, and it becomes difficult to rapidly generate the iodide ion-releasing agent, which is not preferable.

A preferable temperature range is 30 to 80 ° C.,
More preferably 35 to 75 ° C, particularly preferably 35 to 6
It is 0 ° C. When the temperature is higher than 80 ° C., the iodide ion-releasing reaction rate is generally extremely high, and when the temperature is lower than 30 ° C., the iodide ion-releasing reaction rate is generally extremely slow.

When a base is used for releasing iodide ions, a change in liquid pH may be used. At this time, the range of pH is preferably 2 to 12, and more preferably 3 to control the release rate and timing of iodide ions.
11, particularly preferably 5 to 10, and most preferably the adjusted pH is 7.5 to 10.0. Even under neutral conditions of pH 7, the hydroxide ion determined by the ionic product of water acts as a regulator. Further, a nucleophile and a base may be used in combination, and at this time, the pH may be controlled within the above range to control the release rate and timing of iodide ions.

When iodine atoms are released from the iodide ion-releasing agent in the form of iodide ions, all iodine atoms may be released or some of them may remain without being decomposed. A second shell is provided on the tabular grain having the base and the first shell described above. The ratio of the second shell is preferably 10 mol% or more and 40 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 5 mol% or less. More preferably, the ratio of the second shell is 15 mol% or more and 30 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 3 mol% or less. The growth of the second shell on the tabular grains having the base and the first shell may be either in the direction of increasing the aspect ratio of the tabular grains or in the direction of lowering it. Basically, the second shell is grown by adding an aqueous silver nitrate solution and an aqueous halogen solution containing bromide by the double jet method. Alternatively, an aqueous silver nitrate solution may be added by a single jet method after adding an aqueous halogen solution containing bromide. System temperature, pH, type of protective colloid agent such as gelatin, concentration, presence or absence of silver halide solvent,
The type, concentration, etc. can vary widely. For pBr,
In the present invention, it is preferable that pBr at the end of formation of the layer is higher than pBr at the beginning of formation of the layer. Preferably, the pBr at the beginning of formation of the layer is 2.9 or less and the pBr at the end of formation of the layer is 1.7 or more. More preferably, the pBr at the beginning of formation of the layer is 2.5 or less, and the pBr at the end of formation of the layer is 1.9 or more. Most preferably, pBr at the initial stage of formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less.

Dislocation lines are preferably present in the portion of the step (b1). The dislocation lines are preferably present near the edges of tabular grains. The vicinity of the edge portion means the outer peripheral portion (edge portion) of the six sides of the tabular grain and its inner portion, that is, the portion grown in the step (b1). The average number of dislocation lines existing in the edge portion is preferably 10 or more per grain. More preferably, the average number of particles is 20 or more per particle.
When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, approximately 10, 20
It is possible to count as many as 30 books, which can be distinguished from the case where there are obviously only a few books. The average number of dislocation lines per grain is calculated as the number average by counting the number of dislocation lines for 100 grains or more.

The tabular grains of the present invention preferably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably account for 100 to 50% (number) of all grains, more preferably 100 to 70%, and particularly preferably 100. To 90%. When it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when determining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains,
More preferably 200 particles or more, particularly preferably 300 particles.
Observe for more than particles and obtain.

Next, the step (b2) will be described. As a first aspect, a method of dissolving only the vicinity of the apex with iodide ions, as a second aspect, a method of simultaneously adding a silver salt solution and an iodide salt solution, and as a third aspect, There is a method of substantially dissolving only the vicinity of the apex using a silver halide solvent, and a fourth embodiment is a method of converting halogen.

A method of dissolving with iodide ion, which is the first embodiment, will be described.

By adding iodide ions to the base particles, the vicinity of each vertex of the base particles is dissolved and the base particles are rounded. Subsequently, when a silver nitrate solution and a bromide solution or a mixed solution of a silver nitrate solution, a bromide solution and an iodide solution is added at the same time, the grains grow further and dislocations are introduced near the apexes. Regarding this method, reference can be made to JP-A-4-149541 and JP-A-9-189974.

In the present embodiment, the total amount of iodide ions added is a value obtained by dividing the total number of moles of iodide ions by the total number of moles of silver of the base grains and multiplying by 100 to obtain I ₂ (mol%). In this case, it is preferable that (I ₂ −I ₁ ) satisfy 0 to 8 with respect to the silver iodide content I ₁ (mol%) of the base grain in order to obtain effective dissolution according to the present invention. It is more preferably 0 or more and 4 or less.

In this embodiment, the concentration of iodide ion added is preferably low, specifically, 0.2 mol / L.
The following concentrations are preferable, and more preferably 0.
1 mol / L. Further, pAg at the time of adding iodide ion is preferably 8.0 or more, more preferably 8.5 or more.

Subsequent to the dissolution of the apical portion of the base grain by adding iodide ion to the base grain, a silver nitrate solution is added alone, or a silver nitrate solution and a bromide solution or a silver nitrate solution, a bromide solution and an iodide solution are mixed. The liquid is added at the same time to further grow the grains and introduce dislocations near the apexes.

The method of simultaneously adding the silver salt solution and the iodide salt solution, which is the second embodiment, will be described. By rapidly adding the silver salt solution and the iodide salt solution to the base grain, silver iodide or silver halide having a high silver iodide content can be epitaxially formed at the apex of the grain. At this time, the addition rate of the silver salt solution and the iodide salt solution is preferably 0.2 minutes to 0.5 minutes, more preferably 0.5 minutes to 2 minutes. Since this method is described in detail in JP-A-4-149541, it can be referred to.

Subsequent to the dissolution of the apical portion of the base grain by adding iodide ion to the base grain, a silver nitrate solution is added alone or a silver nitrate solution and a bromide solution or a silver nitrate solution, a bromide solution and an iodide solution are mixed. The liquid is added at the same time to further grow the grains and introduce dislocations near the apexes.

The method of using a silver halide solvent, which is the third embodiment, will be described.

When a silver halide solvent was added to a dispersion medium containing a base grain and then a silver salt solution and an iodide salt solution were simultaneously added, silver iodide or iodide was added to the apex of the base grain dissolved by the silver halide solvent. Silver halide having a high silver halide content will grow preferentially. At this time, it is not necessary to rapidly add the silver salt solution and the iodide salt solution. This method is described in detail in JP-A-4-149541, which can be referred to.

Subsequent to the dissolution of the apical portion of the base grain by adding iodide ion to the base grain, a silver nitrate solution is added alone or a silver nitrate solution and a bromide solution or a silver nitrate solution, a bromide solution and an iodide solution are mixed. The liquid is added at the same time to further grow the grains and introduce dislocations near the apexes.

Next, a method involving halogen conversion, which is the fourth embodiment, will be described. An epitaxial growth site supporting agent (hereinafter referred to as a site director), such as a sensitizing dye described in JP-A-58-108526, or a water-soluble iodide is added to the base grains to add silver chloride to the top of the base grains. This is a method of converting silver chloride into silver iodide or silver halide having a high silver iodide content by adding iodide ions after forming epitaxial layers. As the site director, a sensitizing dye, a water-soluble thiocyanate ion, and a water-soluble iodide ion can be used, but an iodide ion is preferable. Iodide ion is 0.0005 to 1 mol% with respect to the base grain, preferably 0.0
01-0.5 mol% is preferable. After adding an optimum amount of iodide ion, silver chloride solution and chloride salt solution are simultaneously added, whereby silver chloride can be epitaxially formed on the apexes of the base grains.

The halogen conversion of silver chloride by iodide ion will be described. A silver halide having a high solubility is converted into a silver halide having a lower solubility by adding a halogen ion capable of forming a silver halide having a lower solubility. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. The silver iodide phase is formed at the top of the base grains by selectively converting the halogenated silver chloride epitaxially grown at the top of the base by iodide ions. Detail is,
It is described in JP-A-4-149541.

Following the halogen conversion of silver chloride epitaxially grown on the apexes of the base grains into a silver iodide phase by adding iodide ions, a silver nitrate solution was added alone, or a silver nitrate solution and a bromide solution or a silver nitrate solution was added. A mixed solution of a bromide solution and an iodide solution is added at the same time to further grow the grains and introduce dislocations in the vicinity of the apexes.

Dislocation lines are preferably present in the portion of step (b2). The dislocation lines are preferably present near the corners of tabular grains. The vicinity of a corner is a three-dimensional area surrounded by a perpendicular line and its side when a perpendicular line is drawn from the center of the straight line connecting the center of the particle and each apex to the x% position. That is the part. The value of x is preferably 50 or more and less than 100, more preferably 75.
It is more than 100 and less than 100. 1 dislocation line exists at the edge
An average of 10 or more particles is preferable. More preferably 1
The average number of particles is 20 or more. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count about 10, 20, or 30 lines, and it can be distinguished from the case where only a few lines obviously exist. The average number of dislocation lines per grain is calculated as the number average by counting the number of dislocation lines for 100 grains or more.

The tabular grain of the present invention preferably has a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably account for 100 to 50% (number) of all grains, more preferably 100 to 70%, and particularly preferably 100. To 90%. When it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when determining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains,
More preferably 200 particles or more, particularly preferably 300 particles.
Observe for more than particles and obtain.

Next, the step (b3) will be described. Regarding the epitaxial formation of silver halide on a base grain, as described in U.S. Pat. No. 4,435,501, iodide ion, aminoazaindene, or a spectral sensitizing dye adsorbed on the base grain surface is used. It has been shown that the silver salt epitaxial film can be formed at a selected site, for example, an edge or a corner of a base grain by the site director of the above. In addition, JP-A-8-6906
In No. 9, silver salt epitaxial is formed at a selected site on the ultrathin tabular grain base, and the chemical sensitization of this epitaxial phase is optimized to achieve high sensitivity. Also in the present invention, it is very preferable to sensitize the base particles of the present invention using these methods. The site director is
Aminoazaindene or a spectral sensitizing dye may be used, an iodide ion or a thiocyanate ion may be used, and they may be used properly or in combination depending on the purpose. By changing the amount of the sensitizing dye, iodide ion and thiocyanate ion added, the silver salt epitaxial formation site can be limited to the edge or corner of the base grain.
The amount of iodide ions added is 0.0005 to 1.0 mol%, preferably 0.00
It is 1 to 0.5 mol%. The amount of thiocyanate ion is 0.01 to 0.2 mol%, preferably 0.02 to 0.1 mol% with respect to the amount of silver of the base grains. After the addition of these site directors, a silver salt solution and a halogen salt solution are added to form a silver salt epitaxial. At this time, the temperature is preferably 40 to 70 ° C, more preferably 45 to 60 ° C. The pAg at this time is preferably 7.5 or less, more preferably 6.5 or less. By using the site director, silver salt epitaxials are formed at the corners or edges of the base particles. The emulsion thus obtained may be sensitized by selectively chemically sensitizing the epitaxial phase as in JP-A-8-69069. However, following the silver salt epitaxial formation, a silver salt solution and a halogen salt solution are added. You may add simultaneously and may make it grow further.
The halogen salt aqueous solution added at this time is preferably a bromide salt solution or a mixed solution of a bromide salt solution and an iodide salt solution. Further, the temperature at this time is preferably 40 to 80 ° C, more preferably 45 to 70 ° C. Also, pA at this time
g is preferably 5.5 or more and 9.5 or less, and 6.0 or more and 9.
It is preferably 0 or less.

The epitaxial film formed in the step (b3) is characterized in that a halogen composition different from that of the base particles is basically formed outside the base particles formed in the step (a). The epitaxial composition is AgC
1, AgBrCl, AgBrClI, AgBrI, Ag
I, AgSCN and the like are preferable. Further, it is more preferable to introduce a "dopant (metal complex)" as described in JP-A-8-69069 into the epitaxial layer. The position of epitaxial growth may be at least a part of the corner portion, edge portion, or main plane portion of the base grain,
It may span multiple locations. It is preferable to take the form of only the corner portion, only the edge portion, or the corner portion and the edge portion.

Dislocation lines may not exist in the step (b3), but it is more preferable that dislocation lines exist. The dislocation lines are preferably present at the junction between the base grain and the epitaxial growth portion, or at the epitaxial portion. The number of dislocation lines existing in the bonding portion or the epitaxial portion is preferably 10 or more on average per grain. More preferably, the average number of particles is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count about 10, 20, or 30 lines, and it can be distinguished from the case where only a few lines obviously exist. The average number of dislocation lines per grain is calculated as the number average by counting the number of dislocation lines for 100 grains or more.

It is preferable that the 6-cyano metal complex is doped when the epitaxial portion is formed. Among the 6-cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferable. The addition amount of the metal complex is 1 per mol of silver halide.
It is preferably in the range of 0 ^{-9 to} 10 ^-2 mol, and more preferably in the range of 10 ^{-8 to} 10 ^-4 mol per mol of silver halide. The metal complex can be dissolved in water or an organic solvent and added. The organic solvent is preferably miscible with water. Examples of organic solvents include alcohols, ethers, glycols, ketones, esters, and amides.

The tabular grains of the present invention preferably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably account for 100 to 50% (number) of all grains, more preferably 100 to 70%, and particularly preferably 100. To 90%. When it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when obtaining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains,
More preferably 200 particles or more, particularly preferably 300 particles.
Observe for more than particles and obtain.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. ;
Various synthetic hydrophilic polymeric substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Can be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin are also used. The types of gelatin include alkali-treated gelatin,
Oxidized gelatin obtained by oxidizing the methionine group in the gelatin molecule with hydrogen peroxide (methionine content of 40 μmol / g or less), amino group-modified gelatin of the present invention (eg, phthalated gelatin, trimellitated gelatin, succinated gelatin, malein). Gelatinized, esterified gelatin) is used. In addition, if necessary, JP-A-11-237704
In the molecular weight distribution measured by the Paggy method described in No. 6, a lime-processed bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more may be used. Also, for example,
European Patent No. 758758 and US Patent No. 5733.
The starch described in No. 718 may be used. Other natural polymers include Japanese Examined Patent Publication No. 7-11550, Research Disclosure Vol. 176, No. 17643 (December 1978)
Month) Section IX. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, an ion exchange method, and an ultrafiltration method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

At the time of forming the particles of the present invention, for example, JP-A-5-173268, JP-A-5-173269 and JP-A-5-173269.
-173270, 5-173227, 6-20
The polyalkylene oxide block copolymers described in Nos. 2258 and 7-175147 or the polyalkylene oxide copolymers described in, for example, Japanese Patent No. 3089578 may be present. The compound may be present at any time during the preparation of particles, but its effect is large when it is used at an early stage of particle formation.

The tabular silver halide grains composed of silver iodobromide or silver chloroiodobromide whose main plane parallel to the silver halide grains used in the present invention is (100) plane silver chloride content of less than 10 mol%. But good.

The (100) tabular grains used in the present invention are 50 to 100%, preferably 70 to 100%, and more preferably 90 to 100% of the total projected area on the average that the main plane is the (100) plane. It consists of tabular grains with an aspect ratio of 2 or more. Grain thickness
It is 0.01 to 0.10 μm, preferably 0.02 to 0.08 μm, more preferably 0.03 to 0.07 μm, and the aspect ratio is 2 to 100, preferably 3 to 50, more preferably 5 to 30. Coefficient of variation of particle thickness (100 of "standard deviation of distribution / average particle thickness")
Fraction, hereinafter referred to as COV.) Is 30% or less, preferably 25% or less, more preferably 20% or less. The smaller the COV., The higher the monodispersity of the grain thickness.

The equivalent circle diameter and thickness of the tabular grains are
A transmission electron microscope (TEM) photograph is taken by the replica method to find the equivalent circle diameter and thickness of each particle. in this case,
The thickness is calculated from the length of the shadow of the replica.
The measurement of COV. In the present invention is a result obtained by measuring at least 600 particles or more.

The composition of the (100) tabular grains is silver chloroiodobromide or silver iodobromide having a silver chloride content of less than 10 mol%. Also, other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver telluride, silver carbonate, silver phosphate, and organic acid silver are contained as separate grains or as a part of silver halide grains. Is also good.

The X-ray diffraction method is known as a method for investigating the halogen composition in the AgX crystal. The X-ray diffraction method is described in detail in Basic Analytical Chemistry Course 24 “X-ray diffraction” and the like. As standard, AgX using Cu Kβ radiation as the radiation source
The diffraction angle of the (420) plane is obtained by the powder method.

When the diffraction nucleus 2θ is obtained, the lattice constant a is obtained from the Bragg equation as follows. 2 d sin θ = λ d = a / (h ² + k ² + l ² ) ^1/2 where 2θ is the diffraction angle of the (hkl) plane, λ is the wavelength of the X-ray, and d is the plane of the (hkl) plane. It is an interval. Since the relationship between the halogen composition of the silver halide solid solution and the lattice constant a is already known (see, for example, “The Theory of Photo” edited by TH James).
graphic Process.4th Ed. (Described in Macmillian New York), the halogen composition can be determined by knowing the lattice constant.

The halogen composition structure of the (100) tabular grain may be any structure. For example, particles having a (core / shell) 2 structure in which the halogen composition of the core and the shell have different halogen compositions and particles having a multi-structure having a core and two or more shells are mentioned as examples. The composition of the core is preferably silver bromide, but is not limited thereto. Further, the shell composition preferably has a higher silver iodide content than the core.

The (100) tabular grains preferably have an average silver iodide content of 2.3 mol or more and a surface average silver iodide content of 8 mol% or more. Further, it is more preferable that the variation coefficient of silver iodide content between grains is less than 20%. The surface silver iodide content can be measured using the XPS described above.

The (6) tabular grains can be classified into the following six types. (1) A particle whose main plane is a right-angled parallelogram. (2)
Of the four corners of the right-angled parallelogram, one or more, preferably
Particles with 1 to 4 missing non-equivalently. That is, [(area of maximum missing part) / area of minimum missing part = particles with K1 of 2 to ∞]],
(3) Particles in which the four corners are equivalently missing (particles in which K1 is smaller than 2), (4) 5 to 100%, preferably 20 to 100% of the side surface area of the missing part is {111. } Grain which is a plane. (5) A particle in which at least two opposite sides of the four sides constituting the principal plane are outwardly convex curves, (6) one or more of the four corners of the right-angled parallelogram, preferably Is a particle in which 1 to 4 particles are missing in the shape of a right-angled parallelogram. These can be confirmed by observation using an electron microscope.

The (100) plane ratio in the crystal habit of the surface of the (100) tabular grain is 80% or more, preferably 90% or more. You can estimate. When the (100) tabular ratio of AgX grains in the emulsion is close to 100%,
The above estimate can be confirmed by the following method.
The method is the method described in the Chemical Society of Japan 1984, No. 6, 942p, and the amount of benzothiacyanine dye is changed to a certain amount of the (100) tabular grains at 40 ° C. for 17 hours. The total surface area of all grains per unit emulsion (S) and the total area of (100) plane (S
1), and based on these values, the formula: S1 / S × 100
(%) Is a method of calculating the (100) plane ratio.

The average equivalent spherical diameter of the (100) tabular grains is preferably less than 0.35 μm. The grain size can be estimated by measuring the projected area and the thickness by the replica method.

The main plane parallel to the silver halide grains used in the present invention is the (111) plane or the (100) plane, the aspect ratio is 2 or more, and at least 80 mol%
Tabular grains containing the above silver chloride may be used.

Special measures are required for producing (111) grains with high silver chloride. Wey US Patent No. 4,
The method of producing high silver chloride tabular grains using ammonia in 399,215 may be used. The method of making high silver chloride tabular grains with thiocyanates may be used in Maskasky US Pat. No. 5,061,617. In the high silver chloride grains shown below, in order to form grains having the (111) plane as the outer surface, a method of adding an additive (crystal habit controlling agent) at the time of grain formation may be used. It is shown below.

[0370] Patent number Crystal habit control agent Inventor   U.S. Pat. No. 4,400,463 Azaindenes + Mascasky                               Thioether peptizer   U.S. Pat. No. 4,783,398 2-4-Dithiazolidinone Mifune, etc.   U.S. Pat. No. 4,713,323 Aminopyrazolopyrimidine muscaski   US Pat. No. 4,983,508 Bispyridinium salt Ishiguro et al.   U.S. Pat. No. 5,185,239 Triaminopyrimidine muscaski   U.S. Pat. No. 5,178,997 7-azaindole type compounds Mascasky   U.S. Pat. No. 5,178,998 Xanthine Mascasky   JP-A-64-70741 Dye Nishikawa et al.   JP-A-3-212639 Aminothioether Ishiguro   JP, 4-283742, A thiourea derivative Ishiguro   JP-A-4-335632 Triazolium salt Ishiguro   JP-A-2-32 Bispyridinium salt Ishiguro   JP, 8-227117, A monopyridinium salt Ozeki, etc.

Regarding the formation of (111) tabular grains, there are known methods using various crystal habit controlling agents as described in the above table. Compound Examples 1 to 42) are preferable, and Japanese Patent Application No. 6-3
Crystal habit controlling agents 1 to 29 described in No. 33780 are particularly preferable. However, the present invention is not limited to these.

The (111) tabular grain is obtained by forming two parallel twin planes. Since the formation of twin planes depends on the temperature, the dispersion medium (gelatin), the halogen concentration, etc., these appropriate conditions must be set. When the crystal habit controlling agent is present at the time of nucleation, the gelatin concentration is preferably 0.1% to 10%. The chloride concentration is 0.01 mol / L or more, preferably 0.03 mol / L or more.

Further, in order to make the particles monodisperse, it is disclosed in JP-A-8-184931 that it is preferable not to use a crystal habit controlling agent at the time of nucleation. When the crystal habit controlling agent is not used during nucleation, the gelatin concentration is 0.03.
% To 10%, preferably 0.05% to 1.0%.
The chloride concentration is 0.001 mol / L to 1 mol / L, preferably 0.003 mol / L to 0.1 mol / L. The nucleation temperature can be selected from 2 ° C to 90 ° C, but 5 ° C to
80 degreeC is preferable and 5 degreeC-40 degreeC is especially preferable.

Nuclei of tabular grains are formed in the initial nucleation stage, and immediately after the nucleation, a large number of nuclei other than tabular grains are contained in the reaction vessel. Therefore, after nucleation, ripening is performed,
It is necessary to have a technique for leaving only tabular grains and extinguishing others. When the normal Ostwald ripening is carried out, the tabular grain nuclei are also dissolved and disappeared, so that the tabular grain nuclei decrease and the size of the resulting tabular grains increases. In order to prevent this, a crystal habit controlling agent is added. In particular, the combined use of phthalated gelatin can enhance the effect of the crystal habit controlling agent and prevent dissolution of tabular grains. The pAg during aging is particularly important and is preferably 60 to 130 mV for silver-silver chloride electrodes.

Next, the formed nuclei are grown in the presence of a crystal habit-controlling agent by physical ripening and addition of a silver salt and a halide. At this time, the chloride concentration is 5 mol / L or less, preferably 0.05 to 1 mol / L. The temperature during grain growth can be selected in the range of 10 ° C to 90 ° C, but 30 ° C to 80 ° C.
Is preferred.

The total amount of the crystal habit controlling agent used is 6 × 10 ⁻⁵ mol or more, and particularly 3 ×, per mol of silver halide in the finished emulsion.
It is preferably 10 ⁻⁴ mol to 6 × 10 ⁻² mol. The crystal habit controlling agent may be added at any time from the nucleation of silver halide grains to the physical ripening or the middle of grain growth. The formation of the (111) plane starts after the addition. The crystal habit controlling agent may be added in advance in the reaction vessel, but when small-sized tabular grains are formed, it is preferably added in the reaction vessel along with grain growth to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to supplement it by addition. Preferably 10 to 100 g / L gelatin is present for growth. As the supplemented gelatin, phthalated gelatin or trimellitic gelatin is preferable. PH during particle formation
Is optional, but a neutral to acidic region is preferable.

The (100) tabular grain will be described below. The (100) tabular grain is a tabular grain having the (100) plane as the main plane. The shape of the main plane is a right-angled parallelogram shape, or a 3-5 pentagonal shape in which one corner of the right-angled parallelogram is missing (a missing shape is a side whose corner is a vertex and which is a corner. A right-angled triangle part) formed by, or 2 or more and 4 or less of the missing parts 4
There are octagonal shapes and the like.

If the right-angled parallelogram shape that has made up for the missing portion is a supplemental quadrilateral, then the ratio of adjacent sides of the right-angled parallelogram and the supplemental quadrilateral (length of long side / length of short side) is 1
-6, preferably 1-4, more preferably 1-2.

The method for forming tabular silver halide emulsion grains having (100) main planes is to add and mix an aqueous silver salt solution and an aqueous halide salt solution in a dispersion medium such as an aqueous gelatin solution while stirring. At this time, for example, JP-A-6-301129 and JP-A-6-347929.
No. 9-34045 and No. 9-96881, silver iodide or iodide ion, or silver bromide or bromide ion is allowed to be present, and a nucleus is formed due to a difference in crystal lattice size from silver chloride. A method of introducing a crystal defect that causes strain and imparts anisotropic growth property such as screw dislocation is disclosed. When the screw dislocations are introduced, the formation of two-dimensional nuclei on that surface is not rate-determining under low supersaturation conditions, so crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocations. To be done. Here, the low supersaturation condition is preferably 35% or less at the time of critical addition, more preferably 2 to
Indicates 20%. Although it has not been determined that the crystal defect is a screw dislocation, it is considered to be highly likely that the crystal defect is a screw dislocation because of the direction in which the dislocation is introduced or the grain is given an anisotropic growth property. In order to make the tabular grains thinner, it is preferable to retain the introduced dislocations.
122954 and 9-189977.

Further, in (JP-A-6-347928), imidazoles and 3,5-diaminotriazoles are used, and in JP-A-8-339044, polyvinyl alcohols are used to form a (100) plane formation accelerator. A method of adding to form (100) tabular grains is disclosed. However, the present invention is not limited to these.

High silver chloride grains have a silver chloride content of 80 mol%.
Although the above-mentioned grains are referred to, it is preferable that 95 mol% or more is silver chloride. The particles of the present invention preferably have a so-called core / shell structure composed of a core portion and a shell portion surrounding the core portion. It is preferable that 90 mol% or more of the core portion is silver chloride. The core part may further be composed of two or more parts having different halogen compositions. The shell portion is preferably 50% or less of the total particle volume, and 2
It is particularly preferably 0% or less. The shell portion is preferably silver iodochloride or silver iodobromochloride. The shell portion preferably contains 0.5 mol% to 13 mol% iodine, and particularly preferably 1 mol% to 13 mol%. The content of silver iodide in all the grains is preferably 5 mol% or less, particularly preferably 1 mol% or less.

The silver bromide content is preferably higher in the shell part than in the core part. The silver bromide content is preferably 20 mol% or less, particularly preferably 5 mol% or less.

The average grain size (volume equivalent sphere equivalent diameter) of silver halide grains is not particularly limited, but is preferably 0.
1 μm to 0.8 μm, particularly preferably 0.1 μm to 0.
It is 6 μm.

The tabular grain of silver halide preferably has a circle equivalent diameter of 0.2 to 1.0 μm. Here, the diameter of silver halide grains means the diameter of a circle having an area equal to the projected area of the grains in an electron micrograph. The thickness is 0.2 μm or less, preferably 0.1 μm or less, and particularly preferably 0.06 μm or less. In the present invention, 50% or more of the projected area of all silver halide grains containing a yellow dye-forming coupler has an average aspect ratio (its diameter / thickness ratio) of 2 or more, preferably 5 or more and 20 or less.

In general, tabular grains are tabular having two parallel planes, and therefore "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular grain.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse, but monodisperse is more preferable. In particular, it is preferable that the coefficient of variation of the circle-equivalent diameter of tabular grains occupying 50% or more of the total projected area is 20% or less. Ideally, it is 0%.

If the crystal habit-controlling agent is present on the surface of the grain even after grain formation, it will affect the adsorption and development of the sensitizing dye. Therefore, it is preferable to remove the crystal habit controlling agent after grain formation. However, when the crystal habit control agent is removed, high silver chloride (1
11) It is difficult for tabular grains to maintain the (111) plane under normal conditions. Therefore, it is preferable to substitute a photographically useful compound such as a sensitizing dye to maintain the grain morphology. This method is described in JP-A-9-80656,
JP-A-9-106026, US Pat. No. 5,221,6
No. 02, No. 5,286,452, No. 5,2
No. 98,387, No. 5,298,388, No. 5,
No. 176,992.

Although the crystal habit controlling agent is desorbed from the grains by the above method, it is preferable to remove the desorbed crystal habit controlling agent to the outside of the emulsion by washing with water. The washing temperature may be a temperature at which gelatin, which is usually used as a protective colloid, does not solidify. As the washing method, various known techniques such as a flocculation method and an ultrafiltration method can be used. The washing temperature is preferably 40 ° C or higher.

Further, the crystal habit controlling agent promotes desorption from particles at low pH. Therefore, the pH of the washing step is preferably low as long as the particles do not aggregate excessively.

The contents relating to the whole emulsion used in the present invention will be described below. The reduction sensitization preferably used in the present invention is a method of adding a reduction sensitizer to silver halide, a low pA of pAg1 to 7 called silver ripening.
It is also possible to select either a method of growing or ripening silver halide grains in a g atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH ripening. Also, two or more of these methods can be used together.

Particularly, the method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. As reduction sensitizers, stannous salt, ascorbic acid and its derivatives, hydroquinone and its derivatives, catechol and its derivatives, hydroxylamine and its derivatives, amines and polyamines, hydrazine and its derivatives, paraphenylenediamine and its derivatives, form Amidinesulfinic acid (thiourea dioxide),
Examples thereof include silane compounds and borane compounds. These reduction sensitizers can be selected and used for the reduction sensitization of the invention, and two or more kinds of compounds can be used in combination. Regarding the method of reduction sensitization, US Pat. No. 2,518,
No. 698, No. 3,201,254, No. 3,41
No. 1,917, No. 3,779,777, No. 3,9
Regarding the method disclosed in JP-A-30,867 and the method of using a reducing agent, JP-B-57-33572 and 58-141.
0, the method disclosed in JP-A-57-179835 can be used. Catechol and its derivatives, hydroxylamine and its derivatives, formamidinesulfinic acid (thiourea dioxide) 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 the range of 10 ^-7 to 10 ^-1 mol per mol of silver halide is suitable.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. In the case of reduction sensitization, it is preferable to use the compound of the general formula (V) or the general formula (VI).

General formula (V)

[Chemical 81]

General formula (VI)

[Chemical formula 82]

In the general formulas (V) and (VI),
W ₅₁ and W ₅₂ represent a sulfo group or a hydrogen atom. However, W
_At least one of ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as ammonium salt. Specific examples of preferred compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-6,7-di Examples thereof include sulfonaphthalene potassium salt. The preferable addition amount may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence / absence of silver halide solvent, type and concentration, etc. The amount used is 0.0005 to 0.5 mol, more preferably 0.003 to 0.02 mol.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54-1019 are known. (A) Organic thioethers described in JP-A No. 54-158917 and JP-A No. 53-824.
No. 08, No. 55-77737, No. 55-2982 and the like, (b) thiourea derivative, JP-A-53-14.
4319 (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A-54-100717, Examples include e) ammonia and (f) thiocyanate.

Particularly preferred solvents are thiocyanate, ammonia and tetramethylthiourea. The amount of solvent used varies depending on the type, but in the case of thiocyanate, the preferred amount is silver halide 1.
It is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added during grain formation, after grain formation, or before chemical sensitization, when grain surface modification or as a chemical sensitizer is used. As described above, a method of doping the entire grain and a method of doping only the core portion of the grain, the shell portion only, or the epitaxial portion can be selected. For example, Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , P
b (CH ₃ COO) ₂ , K ₄ [Fe (CN) ₆ ], (N
H ₄ ) ₄ [Fe (CN) ₆ ], K ₂ IrCl ₆ , (NH ₄ ) ₃
Examples include RhCl ₆ and K ₄ Ru (CN) ₆ . As ligands for coordination compounds, halo, aco, cyano, cyanate,
It can be selected from thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but two or three types
You may use it in combination of 2 or more types.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding a hydrogen halide aqueous solution (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (for example, AgNO3) or an alkali halide aqueous solution (for example, NaCl, K)
It is also possible to add it to Br, KI) and continuously add it during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

The silver halide grain of the present invention has at least one of sulfur sensitization, selenium sensitization, tellurium sensitization and other chalcogen sensitization, gold sensitization and palladium sensitization, and reduction sensitization. It can be applied at any step of the process for producing a silver halide emulsion. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected depending on the purpose, but generally preferred is the case where at least one chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, No. 4. Edition, published by Macmillan, 1
977, (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, Vol. 34, June 1975,
13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, and 4 , 266,018 and 3,904,41
5 and pAg 5-10, pH 5-8 and temperature 30-8 as described in British Patent 1,315,755.
It can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers at 0 ° C. In noble metal sensitization, gold, platinum,
Noble metal salts such as palladium and iridium can be used, and gold sensitization, palladium sensitization, and a combination of both are particularly preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are R
It is represented by ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group.
X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K₂PdCl_Four, (NH_Four)₂Pd
Cl₆, Na₂PdCl_Four, (NH_Four) ₂PdCl_Four, Li₂
PdCl_Four, Na₂PdCl₆Or K₂PdBr_FourIs preferred
Good Thiocyanic acid for gold and palladium compounds
It is preferable to use it together with salt or selenocyanate.
Yes.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,0.
The sulfur-containing compounds described in No. 54,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers include U.S. Pat. "Photographic Emulsion Chemistry", pages 138-143.

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

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 per mol of silver halide.
It is in the range of x10 ^-4 to 1 x 10 ^-7 mol, and more preferably 1 x 10 ^-5 to 1 x 10 ^-7 mol.

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

During the manufacturing process of the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are, for example, silver halide and sulfide.
You may form a sparingly soluble silver salt such as silver or silver selenide.
You may also form a silver salt that is easily soluble in water, such as silver nitrate.
Yes. The oxidizing agent for silver may be an inorganic substance or an organic substance.
It may be. Examples of the inorganic oxidant include azo.
Hydrogen peroxide, hydrogen peroxide and its adducts (eg NaBO₂
・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, Na_FourP₂
O₇・ 2H₂O₂2Na₂SO_Four・ H₂O₂・ 2H₂K₂P₂O
₈), A peroxy complex compound (for example, K ₂[Ti
(O₂) C₂O_Four] ・ 3H₂O, 4K₂SO_Four・ Ti (O₂)
OH / SO_Four・ 2H₂O, Na₃[VO (O₂) (C₂H_Four)
₂] ・ 6H₂O), permanganate (eg, KMn
O_Four), Chromates (eg, K₂Cr₂O₇) Acids like
Halides, halogen elements such as iodine and bromine, perhalogens
Acid salts (eg potassium periodate), of high valent metals
Salts (eg potassium hexacyanoferrate) and thi
There is osphonate.

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

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

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

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, ie, for example, indolenine nuclei, benzoindolenine nuclei, indole nuclei, benzoxador nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei, quinoline nuclei are applied. it can. These nuclei may have a substituent on a carbon atom.

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

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617, 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, British Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
JP-A-58-113928, that spectral sensitization is carried out simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, or the spectral sensitization can be started before the completion of silver halide grain precipitation. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add it after the feeling, and it is possible to add it after the sensation.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756. The addition amount is 4 × 10 ⁻⁶ to 8 × 10 ⁻³ per mol of silver halide.
It can be used in moles.

In the light-sensitive material of the present invention, at least one red photosensitive layer, at least one green photosensitive layer and at least one blue photosensitive layer are provided on a support. Each color-sensitive layer has a light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. In the silver halide color photographic light-sensitive material of the present invention, the unit photosensitive layers are generally arranged in order from the support side to a red color-sensitive layer, a green color-sensitive layer,
They are installed in order of blue color sensitivity. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These include the couplers described below,
A DIR compound, a color mixing inhibitor, etc. may be contained. A plurality of silver halide emulsion layers constituting each unit photosensitive layer,
DE 1,121,470 or GB 923,04
As described in No. 5, it is preferable to arrange two layers, a high-speed emulsion layer and a low-speed emulsion layer, so that the sensitivities of the layers gradually decrease toward the support. Also, JP-A-57-11275
1, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is provided on the side farther from the support and a high-sensitivity emulsion layer is provided on the side closer to the support. Good.

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

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and JP-A-62-63936.
Alternatively, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support, as described in 1.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is further than the middle layer. An example is an arrangement in which a silver halide emulsion layer having low photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support.

Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion is formed from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above.

The silver halide photographic light-sensitive material of the present invention comprises a support, a blue-sensitive silver halide emulsion layer containing at least one layer of a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and cyan. In the case of a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer containing a coupler and a non-photosensitive layer and having a specific sensitivity of 640 or more, the above-mentioned red-sensitive silver halide emulsion layer at 580 nm The spectral sensitivity S _{R (580)} preferably has the following relationship with the spectral sensitivity S _{R (max) at} the highest sensitivity wavelength of the layer. 0.6≤SR _(max) -SR ₍₅₈₀₎ ≤0.9.

The red-sensitive silver halide emulsion layer (as a whole of two or more emulsion layers) has a thickness of 500 nm to 600 nm.
In the range of nm, the centroid sensitivity wavelength (λ _-R ) of the spectral sensitivity distribution of the multi-layer effect received from other layers is 500 nm <λ _-R ≤ 560n
m, the centroid sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer (as a whole of two or more emulsion layers) is 520 nm ≦ λ _G ≦ 580 nm, and λ _G
It is preferable that −λ _−R ≧ 5 nm.

As the sensitizing dye and solid disperse dye used in this case, those described in JP-A No. 11-305396 can be used. The center-of-gravity sensitivity wavelength of the spectral sensitivity distribution of the multi-layer effect which the above-mentioned specific sensitivity and red-sensitive silver halide emulsion layers receive from other layers can be determined by the method described in JP-A No. 11-305396.

The silver halide photographic light-sensitive material of the present invention is red
Spectral sensitivity S of photosensitive layer and green photosensitive layer _{R (580)}, S_{G (580)}But
It is preferable to simultaneously satisfy the following ranges. Where S
_{G (58 0)}, S_{R (580)}Is magenta at each wavelength
The lowest density of cyan color and cyan color, plus a density of 1.0
Defined by the logarithm of the reciprocal of the exposure required to
It S_{G (max)}And S_{R (max)}Are the red light sensitive layer and green
The sensitivity at the maximum sensitivity wavelength of the light layer. Also, spectral sensitivity
Degree changes from underexposed to overexposed
Preferably not. 0.6 ≦ S_{R (max)}-S_{R (580)}≤ 0.9 0.6 ≦ S_{G (max)}-S_{G (580)}≦ 1.1.

The wavelength of the maximum sensitivity of the red photosensitive layer is from 610 nm to 640 nm, preferably 620 nm.
nm to 635 nm. Further, the spectral sensitivity S _{R (650)} of the red photosensitive layer at 650 nm desirably has the following relationship. S _{R (650)} ≦ S _{R (max)} −0.7 Here, the definition of the spectral sensitivity is the same as the above definition.

The wavelength of the maximum sensitivity of the green photosensitive layer is from 520 nm to 580 nm, preferably 540 nm.
nm to 565 nm. Further, the spectral sensitivity S _{G (525)} of the green photosensitive layer at 525 nm desirably has the following relationship. 0.1 ≦ S _{G (max)} −S _{G (525)} ≦ 0.3.

It is preferable to utilize the interlayer suppression effect as a means for improving color reproducibility. Especially, the centroid sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer
Is 520 nm <λ _G ≦ 580 nm, and the wavelength of the center of gravity (λ ₋ of the spectral sensitivity distribution of the magnitude of the interlayer effect that the red-sensitive silver halide emulsion layer receives from other silver halide emulsion layers in the range of 500 nm to 600 nm (λ _{− R} ) is 500 nm <λ _-R
<560 nm, and λ _G −λ _−R is 5 nm or more,
It is preferably 10 nm or more.

In order to give the above-mentioned layering effect to the red-sensitive layer in a specific wavelength region, it is preferable to provide a layering effect donor layer separately containing a predetermined spectrally sensitized silver halide grain. In order to realize the spectral sensitivity of the present invention, the multilayer sensitivity wavelength of the multilayer effect donor layer is 510 nm to 540 n.
set to m.

Here, the red-sensitive silver halide emulsion layer is 50
The centroid wavelength λ of the wavelength distribution of the magnitude of the interlayer effect received from another silver halide emulsion layer in the range of 0 nm to 600 nm
_-R can be determined by the method described in JP-A No. 11-305396. Further, when λ _-B is determined in the same manner as in the procedure for determining λ _-R , the multilayer effect provided by the donor layer must satisfy the condition (formula (2)) described in JP-A-11-305396. .

Further, as a material which gives an interlayer effect, a compound which reacts with an oxidation product of a developing agent obtained by development to release a development inhibitor or a precursor thereof is used. For example, D
IR (development inhibitor releasing type) couplers, DIR-hydroquinone, DIR-hydroquinone or couplers that release their precursors are used. In the case of a development inhibitor having a large diffusivity, the development inhibition effect can be obtained wherever the donor layer is positioned in the multilayer structure, but the development inhibition effect in an unintended direction also occurs, so this is corrected. To develop the donor layer (eg, to the same color as the layer affected by the unwanted development inhibitor).
It is preferable. In order to obtain the desired spectral sensitivity of the light-sensitive material of the present invention, it is preferable that the donor layer that provides the multilayer effect develops magenta color.

The silver halide grains used in the layer that gives the red-sensitive layer a multilayer effect may be any of the grains described above, and the size and shape thereof are not particularly limited. Further, in order to expand the exposure latitude, it is preferable to mix two or more kinds of emulsions having different grain sizes.

The donor layer which gives a multilayer effect to the red-sensitive layer may be coated at any position on the support, but it is coated at a position closer to the support than the blue-sensitive layer and farther from the support than the red-sensitive layer. Preferably. Further, it is more preferably on the side closer to the support than the yellow filter layer.

The donor layer that gives the red-sensitive layer a multilayer effect is preferably closer to the support than the green-sensitive layer and farther from the support than the red-sensitive layer, and closer to the support of the green-sensitive layer. Most preferably, it is located adjacent to the side. In this case, "adjacent" means that no intermediate layer is interposed. The layer that gives the red-sensitive layer a multilayer effect may be composed of a plurality of layers. In that case, those positions may be adjacent to or apart from each other.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

US (US Patent) 4,082,553 silver halide grains having surface-fogged grains, US
No. 4,626,498, and silver halide grains in which the inside of the grains is fogged, colloidal silver as a photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. Is preferably applied to.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is 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
˜0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the mass or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area)
0.01 to 0.5 μm is preferable, and 0.02 to 0.2 μm is more preferable.

Fine grain silver halide can be prepared in the same manner as in ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the fine silver halide grain-containing layer.

Although the above-mentioned various additives are used in the light-sensitive material of the present technology, various additives other than the above can be used according to the purpose. These additives are
For more details, Research Disclosure Item 17
643 (December 1978), Item 18716 (1)
997) and Item 308119 (198).
(December 9th), and the relevant parts are summarized in the table below.

[0440]   Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer Page 23 Page 648 Right column Page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23-24, page 648, right column-996 right-998 right     Supersensitizer, page 649, right column 4 Whitening agents 24 pages 998 Right 5 Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right     And stabilizers 6 Light absorber, page 25-26 page 649 right column-1003 left-1003 right     Filter dye page 650, left column     UV absorber 7 Anti-stain agent Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer 25 pages 1002 right 9 Hardener 26 pages 651 left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, Lubricant Page 27 Page 650 Right column 1006 Left to 1006 Right 12 Coating aid, pages 26-27 Same as above 1005 left to 1006 left     Surfactant 13 Static 27 pages Same as above 1006 right to 1007 left     Preventive agent 14 Matting agent 1008 left to 1009 left.

Techniques such as layer arrangement which can be used for the photographic light-sensitive material of the present invention and the emulsion usable in the light-sensitive material, silver halide emulsion, dye-forming coupler, DI
Functional couplers such as R couplers, various additives, and development processing are described in European Patent No. 0565096A1 (published on October 13, 1993) and the patents cited therein. Below, each item and the corresponding description place are listed.

1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14; Middle layer: p. 61, lines 36-40, 3. Multilayer effect imparting layer: p. 62, lines 15-18, 4. 4. Silver halide halogen composition: page 62, lines 21-25, 5. Silver halide grain crystal habit: p. 62, lines 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion production method: Page 62, lines 35-40, 8. Silver halide grain size distribution: p. 62 41-42
Line, 9. Tabular grains: Page 62, lines 43-46, 10. Internal structure of particles: p. 62, lines 47-53, 11. Emulsion latent image forming type: page 62 line 54 to page 63 5
Line, 12. Physical ripening / chemical sensitization of emulsion: page 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogging emulsion: page 63, lines 14-31, 15. Non-light-sensitive emulsion: page 63, lines 32-43, 16. Amount of coated silver: p. 63, lines 49-50, 17. Formaldehyde Scavenger: 64 pages 54-5
7 lines, 18. Mercapto-based antifoggant: Page 65, lines 1-2, 19. Release agents such as fogging agents: p. 65, lines 3-7, 20. Dye: Page 65, lines 7-10, 21. Color couplers in general: Page 65, lines 11-13, 22. Yellow, magenta and cyan couplers: p. 65 1
Lines 4-25, 23. Polymer coupler: page 65, lines 26-28, 24. Diffusible dye-forming coupler: p. 65, lines 29-31, 25. Colored coupler: page 65, lines 32-38, 26. Functional couplers in general: Page 65, lines 39 to 44, 27. Bleach accelerator releasing coupler: page 65, lines 45-48, 28. Development accelerator releasing coupler: p. 65, lines 49-53, 29. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 30. Coupler dispersion method: Page 66, lines 5 to 28, 31. Preservatives and fungicides: 66, lines 29-33, 32. Kind of sensitive material: page 66, lines 34-36, 33. Photosensitive layer film thickness and swelling speed: page 66 line 40 to page 67 1
Line, 34. Back layer: Page 67, lines 3-8, 35. General development processing: Page 67, lines 9-11, 36. Developer and developer: p. 67, lines 12-30, 37. Developer additive: p. 67, lines 31-44, 38. Inversion processing: Page 67, lines 45-56, 39. Treatment liquid opening ratio: page 67, line 57 to page 68, line 12, 40. Development time: page 68, lines 13-15, 41. Bleach-fix, bleach-fix, page 68, line 16 to page 69, 31.
Line, 42. Automatic developing machine: 69 pages, lines 32-40, 43. Washing, rinsing, stabilizing: page 69 line 41 to page 70 18
Line, 44. Replenishment and reuse of processing liquid: Page 70, lines 19-23, 45. Built-in developer sensitive material: page 70, lines 24-33, 46. Development processing temperature: Page 70, lines 34-38, 47. Use for film with lens: Page 70, lines 39-41.

Also, a bleaching solution containing 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate described in European Patent No. 602600 can be used. It can be preferably used. In the use of this bleaching solution, it is preferable to interpose a stopping step and a water washing step between the color developing step and the bleaching step,
It is preferable to use organic acids such as acetic acid, succinic acid, and maleic acid as the stop solution. Furthermore, this bleach solution contains p
For the purpose of H adjustment and bleaching fog, organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, and adipic acid are added in an amount of 0.1 to 0.1%.
It is preferably contained in the range of 2 mol / L.

Next, the magnetic recording layer preferably used in the present invention will be described. The magnetic recording layer preferably used in the present invention is a layer in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support.

The magnetic particles used in the present invention are γFe ₂ O
Ferromagnetic iron oxide such as _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal system Ba ferrite, Sr ferrite, Pb ferrite , Ca ferrite, etc. can be used. Co-deposited ferromagnetic iron oxides such as Co-deposited γFe ₂ O ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 ×
10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-101632. In addition, JP-A-4-25
Inorganic on the surface described in No. 9911 and No. 5-81652,
Magnetic particles coated with an organic substance can also be used.

The binder used in the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the mass average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate and other cellulose derivatives, acrylic resins, polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable.
The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent.
Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). Examples thereof include a reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane, and polyisocyanate produced by condensation of these isocyanates, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles and the binder is preferably 0.5:
It is composed of 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably
It is 0.01 to ² g / m ² , and more preferably 0.02 to 0.5 g / m ² .
The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in the form of a stripe. As a method for applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss, a cast, a spray, a dip, a bar, an extrusion and the like can be used. The coating solutions described in JP-A-341436 and the like are preferable.

For the magnetic recording layer, improved lubricity, curl adjustment,
It may have functions such as antistatic, adhesion prevention, and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and preferably the same binder as that of the magnetic recording layer is used. US Pat. No. 5,336,589, US Pat. No. 5,250,404, US Pat.
5,229,259 and 5,215,874, EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details, including the light-sensitive material, processing, cartridge and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3.15.). The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components. As the aromatic dicarboxylic acid, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid are used. Examples of the acid, isophthalic acid, phthalic acid and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, particularly preferred is polyethylene-2,
It is 6-naphthalate. Average molecular weight range is about 5,000
To 200,000. Polyester T used in the present invention
The g is 50 ° C or higher, preferably 90 ° C or higher.

Next, the polyester support has a curl habit.
In order to make it difficult to heat, the heat treatment temperature should be 40 ° C or higher and lower than Tg.
More preferably, the heat treatment is carried out at Tg-20 ° C or higher and lower than Tg.
The heat treatment may be carried out at a constant temperature within this temperature range,
You may heat-process, cooling. This heat treatment time is 0.
1 hour or more and 1500 hours or less, more preferably 0.5 hours or more
It is less than 200 hours. The heat treatment of the support is roll-like and practical.
It may be applied, or it may be carried out in web form.
Good. Unevenness is added to the surface (eg SnO₂And Sb₂O _FiveGuidance of etc.
Electrolytic inorganic fine particles may be applied), and the surface condition may be improved.
Yes. In addition, knurling is added to the ends so that only the ends are slightly raised.
By doing so, we will take measures such as preventing the cut end of the core from appearing.
Is desirable. These heat treatments are performed on the surface after the support is formed into a film.
After processing, after applying the back layer (antistatic agent, slip agent, etc.), below
It may be carried out at any stage after coating. Preferred
Is after application of the antistatic agent.

An ultraviolet absorber may be kneaded into this polyester. In order to prevent light piping, it is possible to achieve the object by kneading commercially available dyes or pigments for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable.

Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer,
Starting with copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethyleneimine, epoxy resin, grafting Examples thereof include gelatin, nitrocellulose, and gelatin.
Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, as a gelatin hardening agent, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Further, in the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acids and carboxylates, polymers containing sulfonates,
Examples thereof include cationic polymers and ionic surfactant compounds.

The most preferable antistatic agent is Zn.
O, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO ₂, MgO, BaO, Mo
O₃, V₂O_FiveAt least one volume resistivity selected from
Ten⁷Ω · cm or less, more preferably 10^FiveGrains that are Ω · cm or less
Child size 0.001-1.0μm Crystalline metal oxide or
These complex oxides (Sb, P, B, In, S, Si, C, etc.)
Particles, sol-like metal oxides, or composites of these
Fine particles of oxide.

The content in the light-sensitive material is 5 to 500 mg / m²But
Particularly preferably 10 to 350 mg / m ²Is. Conductive
Ratio of crystalline oxide or its composite oxide to binder
Is preferably 1/300 to 100/1, more preferably 1/100 to 100
/ 5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. The preferred sliding property is a dynamic friction coefficient of 0.
25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the photosensitive material surface is replaced as the mating material, the values are almost the same.

The slip agents that can be used in the present invention include polyorganosiloxane, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like, and polyorganosiloxanes such as polydimethylsiloxane and polydiethylsiloxane. Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The photosensitive material of the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.1.
It is preferable that 90% or more of the total number of particles be contained during the doubling. In addition, it is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property, for example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Polystyrene particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge used in the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537,
No. 1-312538. 25 ° C, 25
The resistance at% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. The size of the patrone may be the same size as the current 135 size, or the size of the current 135 size is 25m for the miniaturization of the camera.
It is also effective to set the diameter of the m cartridge to 22 mm or less. The volume of the case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the cartridge and cartridge case is 5g.
~ 15g is preferred.

Further, the cartridge used in the present invention may be a cartridge that rotates the spool to feed the film. Further, the film tip may be housed in the cartridge body, and the film tip may be sent to the outside from the port section of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in US 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a developed photographic film. Also, raw film and developed photographic film may be stored in the same new cartridge,
Different patrones may be used.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for advanced photo system (hereinafter referred to as AP system), and can be manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film) NEXIA A, NEXIA
Examples include F and NEXIA H (ISO 200/100/400 in order), which are processed into AP system format and stored in a special cartridge. These AP system cartridge films are used by being loaded into AP system cameras such as the Fuji Film Epion series (Epion 300Z). Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as Fuji Color Fujirun Super Slim made by Fuji Film.

The film photographed by these is printed in the minilab system through the following steps.

(1) Reception (keep the exposed cartridge film from the customer) (2) Detach process (transfer the film from the cartridge to the intermediate cartridge for the development process) (3) Film development (4) Rear touch process (development) Return the used negative film to the original cartridge. (5) Print (C / H / P3 type prints and index prints on color paper [preferably made by FUJIFILM.
SUPER FA8] continuous automatic printing) (6) Verification / shipment (cartridge and index prints are verified by ID number and shipped together with prints).

As these systems, Fuji Film Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as a minilab champion film processor
362B, AL are listed, and recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A /
PP1258AR / PP1258A / PP728AR / PP728A are listed, and recommended treatment chemicals are Fuji Color Justit CP-47L and CP-4.
It is 0FAII.

For Frontier System, Scanner &
Image Processor SP-1000 and Laser Printer &
Paper processor LP-1000P or laser printer LP-1000W is used. The detacher used in the detaching process and the rear toucher used in the rear attaching process are
Fuji Film DT200 / DT100 and AT200 / AT100 are preferable, respectively.

The AP system can also be enjoyed by a photo joy system centered on Fuji Film's digital image workstation Aladdin 1000. For example, you can directly load the developed AP system cartridge film on the Aladdin 1000, or use the 35mm film scanner FE to display the image information of negative film, positive film, and print.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are digital color printer NC-550AL by photo-fixing type thermal color printing system and Pictrography 3000 by laser exposure thermal development transfer system.
Or as a print by existing lab equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is used as a photo player AP made by FUJIFILM.
-You can enjoy photos on TV just by loading it in -1,
By loading it on the Fujifilm Photo Scanner AS-1, it is possible to transfer image information to a PC continuously at high speed. In addition, to input film, prints or three-dimensional objects to a personal computer, you can use FUJIFILM Photo Vision FV-10 / FV.
-5 available. Furthermore, the image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be processed in various ways on a personal computer using Fujifilm's application software Photo Factory and can be enjoyed. To output high-quality prints from a personal computer, Fuji Film's digital color printer NC-2 / NC-2D, which is a light-fixing thermal color printing system, is suitable.

To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferable.

[0471]

EXAMPLES Examples of the present invention will be shown below. However, the present invention is not limited to this embodiment.

(Example 1) Silver halide emulsions Em-A1, A2, B to P, Q1 to T1 and Q2 were prepared by the following production method.
T2 was prepared. (Em-A1) (Emulsion for high-sensitivity blue-sensitive layer) 42.2 L of an aqueous solution containing 29.7 g of phthalated low molecular weight gelatin having a molecular weight of 15,000 and 31.7 g of KBr having a phthalation ratio of 97% was vigorously stirred at 35 ° C. . AgN
1583 mL of an aqueous solution containing 329.7 g of O ₃ and KB
r, 221.5 g, and 1583 mL of an aqueous solution containing 52.7 g of low molecular weight gelatin having a molecular weight of 15,000 were added by the double jet method over 1 minute. KB immediately after addition
In addition to 52.8 g of r2, 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by the double jet method. Immediately after the addition was completed, KBr (47.8 g) was added. Then, the temperature was raised to 40 ° C., and aging was performed sufficiently. After aging, the phthalated molecular weight is 1,000 with a phthalated ratio of 97%.
923 g of gelatin and 00,79.2 g of KBr, and an aqueous solution containing 5,103 g of AgNO ₃ , 15947 m
The L and KBr aqueous solutions were added by the double jet method over 12 minutes while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the silver potential was kept at -55 mV with respect to the saturated calomel electrode. After washing with water, add gelatin and p
A seed emulsion was prepared by adjusting H, 5.7, pAg, and 8.8 to a mass of 131.8 g in terms of silver per 1 kg of emulsion and a mass of gelatin of 64.1 g.

Phthalated gelatin with a phthalation ratio of 97% 46
g, KBr 1.7g aqueous solution 1211mL containing 75g
And kept vigorously stirred. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicon oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adding H ₂ SO ₄ to adjust the pH to 5.5, AgNO ₃ , 7.0 g
67.6 mL of an aqueous solution containing K and an aqueous KBr solution were added by a double jet method over 6 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV against the saturated calomel electrode. Sodium benzenethiosulfonate, 2 mg and thiourea dioxide 2
After adding mg, an aqueous solution containing AgNO ₃ , 134.4 g, an aqueous solution of 381 mL and an aqueous solution of KBr were added by the double jet method for 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. . At this time, 0.037 μm
AgI fine grain emulsion having a grain size of
The flow rate was simultaneously accelerated and added so that the concentration became mol%, and the silver potential was maintained at −30 mV with respect to the saturated calomel electrode. 121.3 m of an aqueous solution containing 45.6 g of AgNO ₃ .
The L and KBr aqueous solutions were added by the double jet method over 22 minutes. At this time, the silver potential was kept at +20 mV against the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then an AgI fine grain emulsion having a grain size of 0.037 μm was converted to a KI mass of 6.3.
3 g was added. Immediately after the addition was completed, AgNO ₃ , 6
206.2 mL of an aqueous solution containing 6.4 g was added over 16 minutes. The silver potential was kept at -80 mV with an aqueous KBr solution for 5 minutes at the initial stage of the addition. After washing with water, gelatin containing 30% of a component having a molecular weight of 280,000 or more when measured according to the PAGI method was added, and the pH was adjusted to 5.8, pAg, and 8.7 at 40 ° C. After adding the compounds 11 and 12, the temperature was raised to 60 ° C. After adding the sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
Optimum chemical sensitization was performed by adding N, N-dimethylselenourea. After completion of the chemical sensitization, compounds 13 and 14 were added. Here, optimum chemical sensitization means that the sensitizing dye and each compound are added in an amount of 10 ^-1 to 10 ^-8 per mol of silver halide.
This means that the addition amount range of moles was selected. Compound 11

[Chemical 83]

Compound 12

[Chemical 84]

Compound 13

[Chemical 85]

Compound 14

[Chemical 86]

Sensitizing Dye 11

[Chemical 87]

Sensitizing dye 12

[Chemical 88]

As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the periphery of the particles.

(Em-Q1) An emulsion Em-Q1 was prepared in the same manner as Em-A1 except that the compound (I-19) of the present invention was added at 1 × 10 ^-4 mol / molAg during the chemical sensitization.

(Em-R1) An emulsion Em-R1 was prepared in the same manner as Em-A1 except that the compound (I-20) of the present invention was added at 1 × 10 ^-4 mol / mol Ag during the chemical sensitization.

(Em-S1) An emulsion Em-S1 was prepared in the same manner as Em-A1 except that the compound (I-53) of the present invention was added at 1 × 10 ^-4 mol / mol Ag during the chemical sensitization.

(Em-T1) E except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-1) of the present invention was added during chemical sensitization.
Emulsion Em-T1 was obtained in the same manner as m-A1.

(Em-A2) (Emulsion for high-sensitivity blue-sensitive layer) After adding 9.1 g of the above-mentioned seed emulsion, 0.3% of modified silicone oil (manufactured by Nippon Unica Co., Ltd., L7602) was added.
g was added. After H ₂ SO ₄ was added to adjust the pH to 5.5, 67.6 mL of an aqueous solution containing AgNO ₃ and 7.0 g
And KBr aqueous solution were added by the double jet method over 6 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was changed with respect to the saturated calomel electrode −
It was kept at 35 mV. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, A
An aqueous solution containing 134.4 g of gNO ₃ , 381 mL and K
The aqueous solution of Br was added by the double jet method over 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, AgI having a particle size of 0.037 μm
The fine grain emulsion was added at the same time by accelerating the flow rate so that the silver iodide content was 7 mol%, and the silver potential was kept at -30 mV with respect to the saturated calomel electrode. AgNO ₃ , 10
330.8 mL of an aqueous solution containing 2.4 g and a KBr aqueous solution were added by the double jet method over 60 minutes. At this time,
The silver potential is + for the first 50 minutes against a saturated calomel electrode.
The voltage was kept at 10 mV and 90 mV for the remaining 10 minutes. Fifty
After cooling to 0 ° C, 55 mL of 0.3% KI aqueous solution was added over 10 minutes. Immediately thereafter, 14.2 g of AgNO ₃
Aqueous solution containing 100 mL, NaCl 2.1 g, KBr
Aqueous solution 120 mL containing 4.17 g and AgI fine particles 0.0
A solution containing 133 mol was added simultaneously. At this time, 9.4 × 10 ⁻⁴ m for 1 mol of AgNO ₃ added
ol K ₄ [RuCN ₆ ] was present. Then a sensitizing dye was added (for epitaxial stabilization). After washing with water, when the molecular weight distribution was measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added, and the pH was adjusted to 5.8, pAg, and 8.7 at 40 ° C. The subsequent process performed the same process as Em-A1.

Observation of the obtained grains with a scanning electron microscope revealed that an epitaxial layer was attached to the apexes of the tabular grains.

(Em-Q2) An emulsion Em-Q2 was obtained in the same manner as Em-A2, except that the compound (I-19) of the present invention was added at 1.2 × 10 ⁻⁴ mol / molAg during the chemical sensitization. It was

(Em-R2) An emulsion Em-R2 was obtained in the same manner as Em-A2 except that the compound (I-20) of the present invention was added at 1.2 × 10 ^-4 mol / mol Ag during the chemical sensitization. .

(Em-S2) An emulsion Em-S2 was obtained in the same manner as Em-A2 except that the compound (I-53) of the present invention was added at 1.2 × 10 ⁻⁴ mol / mol Ag during the chemical sensitization. .

(Em-T2) An emulsion Em-T2 was obtained in the same manner as Em-A2 except that the compound (I-1) of the present invention was added at 1.2 × 10 ⁻⁴ mol / molAg during the chemical sensitization. .

(Em-B) (Emulsion for Low Sensitivity Blue Sensitive Layer) 1192 mL of an aqueous solution containing 0.96 g of low molecular weight gelatin, 0.9 g of KBr was kept at 40 ° C. and vigorously stirred.
37.5 mL of an aqueous solution containing 1.53 g of AgNO ₃ and K
37.5 mL of an aqueous solution containing 1.5 g of Br was added over 30 seconds by the double jet method. After 1.2 g of KBr was added, the temperature was raised to 75 ° C. for aging. After aging sufficiently, the amino group was chemically modified with trimellitic acid to give a molecular weight of 1000
Add 00g of trimellitated gelatin, 30g, add pH
Was adjusted to 7. 6 mg of thiourea dioxide was added. A
116 mL of an aqueous solution containing 29 g of gNO ₃ and a KBr aqueous solution were added by a double jet method while accelerating the flow rate so that the final flow rate was 3 times the initial flow rate. At this time, the silver potential was kept at -25 mV against the saturated calomel electrode. AgN
440.6 mL of an aqueous solution containing 110.2 g of O ₃ and KB
The aqueous r solution was added by the double jet method over 30 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously accelerated and added so that the silver iodide content became 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. It was AgNO ₃ , 24.1
96.5 mL of an aqueous solution containing g and a KBr aqueous solution were added over 3 minutes by the double jet method. At this time, set the silver potential to 0
kept at mV. Sodium ethylthiosulfonate, 26
After adding mg, the temperature was lowered to 55 ° C. and an aqueous KBr solution was added to adjust the silver potential to −90 mV. 8.5 g of the AgI fine grain emulsion described above was added in terms of KI mass. Immediately after the addition is completed, 228 mL of an aqueous solution containing 57 g of AgNO ₃ .
Was added over 5 minutes. At this time, an aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. Em
It was washed with water and chemically sensitized in the same manner as in -A1.

(Em-C) (Emulsion for low-sensitivity blue sensitive layer) 1192 m of an aqueous solution containing 1.02 g of phthalated gelatin having a phthalation ratio of 97% and a molecular weight of 100,000 containing 35 μmol of methionine per 1 g of 0.97 g of KBr.
L was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.
An aqueous solution containing 47 g, 42 mL and KBr, an aqueous solution containing 3.16 g, 42 mL were added over 9 seconds by the double jet method. After 2.6 g of KBr was added, the temperature was raised to 66 ° C. and aged sufficiently. After ripening, trimellitated gelatin 4 having a molecular weight of 100,000 used in the preparation of Em-B
1.2 g and NaCl, 18.5 g were added. After adjusting the pH to 7.2, dimethylamine borane, 8 mg was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ .
And the KBr aqueous solution were added by the double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at -30 mV against the saturated calomel electrode. AgN
440.6 mL of an aqueous solution containing 110.2 g of O ₃ and KB
The aqueous solution of r was accelerated by the double jet method so that the final flow rate was 5.1 times the initial flow rate, and added over 24 minutes. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added while accelerating the flow rate so that the silver iodide content was 2.3 mol%, and the silver potential was set to −20 mV with respect to the saturated calomel electrode. I kept it. After adding 10.7 mL of 1N potassium thiocyanate aqueous solution, AgN
153.5 mL of an aqueous solution containing 24.1 g of O ₃ and KBr
The aqueous solution was added over 2 minutes and 30 seconds by the double jet method. At this time, the silver potential was kept at 10 mV. The silver potential was adjusted to -70 mV by adding a KBr aqueous solution. A mentioned above
6.4 g of gI fine grain emulsion was added in terms of KI mass. Immediately after the addition is complete, an aqueous solution 40 containing 57 g of AgNO ₃ 40
4 mL was added over 45 minutes. At this time, an aqueous KBr solution was adjusted so that the potential at the end of the addition was −30 mV. It was washed with water and chemically sensitized in the same manner as Em-A1.

(Em-D) (Low Sensitivity Blue Sensitive Layer Emulsion) In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.0 times. And the final AgNO ₃ , 57
The potential at the end of addition of 404 mL of an aqueous solution containing g is +90.
It was changed to adjust with an aqueous solution of KBr so as to be mV. Otherwise, it was prepared in substantially the same manner as Em-C.

(Em-E) (magenta color-developing layer having a spectral sensitivity peak at 480 to 550 nm) (Layer that gives an overlapping effect to the red-sensitive layer) Low molecular weight gelatin having a molecular weight of 15,000, 0.71 g, K
Br, 0.92 g, 1200 mL of an aqueous solution containing 0.2 g of the modified silicone oil used in the preparation of Em-A1 was added to 39
The temperature was kept at ℃, the pH was adjusted to 1.8, and the mixture was vigorously stirred. Ag
An aqueous solution containing 0.45 g of NO ₃ and K of 1.5 mol%
The KBr aqueous solution containing I was added by the double jet method over 17 seconds. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 56 ° C. and aging was carried out. After aging sufficiently, a molecular weight of 100 containing 35 μmol of methionine per 1 g
17 g of phthalated gelatin having a phthalation ratio of 97% of 97% was added. After adjusting the pH to 5.9, KBr, 2.9
g was added. Aqueous solution 2 containing 28.8 g of AgNO ₃ .
88 mL and a KBr aqueous solution were added by the double jet method over 53 minutes. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at -70 mV with respect to the saturated calomel electrode. After adding 2.5 g of KBr, an aqueous solution containing 87.7 g of AgNO ₃ and KB
The r aqueous solution was accelerated by the double jet method so that the final flow rate was 1.2 times the initial flow rate, and added over 63 minutes. At this time, the above AgI fine grain emulsion was simultaneously added while accelerating the flow rate so that the silver iodide content was 10.5 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 25 minutes by the double jet method. The potential at the end of addition is +2
The addition of the KBr aqueous solution was adjusted so as to be 0 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After KBr was added to adjust the silver potential to −70 mV, the above AgI fine grain emulsion was added in an amount of 5.73 g in terms of KI mass. Immediately after the addition was completed, 1 609 mL of an aqueous solution containing 66.4 g of AgNO _{3 was} added.
Added over 0 minutes. During the initial 6 minutes of the addition, the silver potential was maintained at -70 mV with a KBr aqueous solution. After washing with water, gelatin was added and the pH was adjusted to 6.5, pAg, and 8.2 at 40 ° C. After adding the compounds 11 and 12, the temperature was raised to 56 ° C. Sensitizing dyes 13 and 14 were added after 0.0004 mol of AgI fine grain emulsion described above was added to 1 mol of silver. Optimum chemical sensitization was performed by adding potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea. Compound 13 at the end of chemical sensitization
And 14 were added.

Sensitizing Dye 13

[Chemical 89]

Sensitizing Dye 14

[Chemical 90]

(Em-F) (Emulsion for Medium-Sensitivity Green Sensitive Layer) Prepared in substantially the same manner as Em-E except that the amount of AgNO ₃ added during nucleation was changed to 3.1 times in the preparation of Em-E. did. However, Em-E sensitizing dyes are used as sensitizing dyes 15 and 16
And changed to 17. Sensitizing dye 15

[Chemical Formula 91]

Sensitizing dye 16

[Chemical Formula 92]

Sensitizing dye 17

[Chemical formula 93]

(Em-G) (Emulsion for low sensitivity green sensitive layer) Low molecular weight gelatin having a molecular weight of 15,000 0.70 g, KB
r, 0.9 g, KI, 0.175 g, an aqueous solution 1 containing 0.2 g of the modified silicone oil used in the preparation of Em-A1
200 mL was maintained at 33 ° C., pH was adjusted to 1.8, and the mixture was vigorously stirred. An aqueous solution containing 1.72 g of AgNO ₃ and a KBr aqueous solution containing 3.2 mol% of KI were added by the double jet method over 9 seconds. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 69 ° C. for aging. After completion of the ripening, 27.8 g of trimellited gelatin in which an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per 1 g was chemically modified with trimellitic acid was added. After adjusting the pH to 6.3, 2.9 g of KBr was added. Aqueous solution 270 containing 27.58 g of AgNO ₃ .
mL and the KBr aqueous solution were added by the double jet method over 37 minutes. At this time, a low molecular weight gelatin aqueous solution having a molecular weight of 15,000, an AgNO ₃ aqueous solution and a KI aqueous solution were prepared.
No. 0-43570, a AgI fine grain emulsion having a grain size of 0.008 μm prepared by mixing just before addition in a separate chamber having a magnetic coupling induction stirrer to a silver iodide content of 4.1 mol%. Are added simultaneously so that the silver potential is −50 mV with respect to the saturated calomel electrode.
Kept at. After adding 2.6 g of KBr, AgN
An aqueous solution containing 87.7 g of O ₃ and an aqueous KBr solution were added by the double jet method over 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing just before the addition was accelerated at the same time so that the silver iodide content was 7.9 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by the double jet method. +20 at the end of addition
The addition of the KBr aqueous solution was adjusted so as to reach mV. 78
After raising the temperature to ℃ and adjusting the pH to 9.1, KBr was added to bring the potential to -60 mV. The AgI fine grain emulsion used in the preparation of Em-A1 was added in an amount of KI in an amount of 5.73 g. Immediately after the addition was completed, 321 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 4 minutes. The silver potential was kept at -60 mV with an aqueous KBr solution for 2 minutes at the initial stage of the addition. It was washed with water and chemically sensitized in the same manner as Em-F.

(Em-H) (Emulsion for low-sensitivity green-sensitive layer) Ion-exchanged gelatin having a molecular weight of 100,000 17.8
An aqueous solution containing g, KBr, 6.2 g, KI, 0.46 g was kept at 45 ° C. and vigorously stirred. AgNO ₃ , 11.8
An aqueous solution containing 5 g and an aqueous solution containing 3.8 g of KBr were added by the double jet method over 47 seconds. Gelatin 2 with a molecular weight of 100,000 was ion-exchanged after heating to 63 ° C.
4.1 g was added and aged. AgN after fully aged
An aqueous solution containing 133.4 g of O ₃ and an aqueous KBr solution were added by a double jet method over 20 minutes so that the final flow rate was 2.6 times the initial flow rate. At this time, the silver potential was kept at +40 mV against the saturated calomel electrode. 10 minutes after the start of addition, 0.1 mg of K ₂ IrCl ₆ was added. Na
After adding 7 g of Cl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added by the double jet method over 12 minutes. At this time, the silver potential was maintained at +90 mV.
Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. After adding 14.4 g of KBr, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition was completed, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was maintained at +90 mV. It was washed with water and chemically sensitized in the same manner as Em-F.

(Em-I) (Emulsion for Low Sensitivity Green Sensitive Layer) It was prepared in the same manner as in Em-H except that the temperature at the nucleation was changed to 38 ° C.

(Em-J) (Emulsion for high-sensitivity red-sensitive layer) Aqueous solution 1 containing phthalated gelatin having a phthalation ratio of 97% and a molecular weight of 100,000, 0.38 g, KBr, and 0.99 g.
200 mL was maintained at 60 ° C., pH was adjusted to 2 and vigorously stirred. Aqueous solution containing 1.91 g of AgNO ₃ and KB
An aqueous solution containing r, 1.97 g, KI, and 0.172 g was added over 30 seconds by the double jet method. After completion of the ripening, 12.8 g of trimellited gelatin in which an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per 1 g was chemically modified with trimellitic acid was added.
After adjusting the pH to 5.9, KBr, 2.99 g, Na
6.2 g of Cl were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at -50 mV against the saturated calomel electrode. AgNO ₃ ,
An aqueous solution containing 65.6 g and a KBr aqueous solution were added by the double jet method over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, Em-A1
The AgI fine grain emulsion used in the preparation of (1) was simultaneously added while accelerating the flow rate so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. After adding thiourea dioxide, 1.5 mg, AgNO ₃ , 41.8 g
132 mL of an aqueous solution containing the above and a KBr aqueous solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to −100 mV. The above AgI fine grain emulsion was converted to 6.2 in terms of KI mass.
g was added. Immediately after the addition, AgNO ₃ , 88.5
300 mL of an aqueous solution containing g was added over 8 minutes. The potential was adjusted to +60 mV by the addition of an aqueous KBr solution at the end of the addition. After washing with water, add gelatin to 40
The pH was adjusted to 6.5 and pAg, 8.2 at ℃. Compound 1
After adding 1 and 12, the temperature was raised to 61 ° C. After adding the sensitizing dyes 18, 19, 20 and 21, K ₂ Ir
Optimum chemical sensitization was performed by adding Cl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea. Compounds 13 and 1 at the end of chemical sensitization
4 was added.

Sensitizing Dye 18

[Chemical 94]

Sensitizing dye 19

[Chemical 95]

Sensitizing dye 20

[Chemical 96]

Sensitizing dye 21

[Chemical 97]

(Em-K) (Emulsion for medium-sensitive red-sensitive layer) Low molecular weight gelatin having a molecular weight of 15,000, 4.9 g, KB
1200 mL of an aqueous solution containing r and 5.3 g was kept at 60 ° C. and vigorously stirred. 27 mL of an aqueous solution containing 8.75 g of AgNO ₃ and 36 mL of an aqueous solution containing 6.45 g of KBr were added over 1 minute by the double jet method. After heating to 77 ° C., 21 mL of an aqueous solution containing AgNO ₃ , 6.9 g
Was added over 2.5 minutes. NH ₄ NO ₃ , 26g, 1
After N, NaOH and 56 mL were sequentially added, the mixture was aged. After the aging, the pH was adjusted to 4.8. AgNO ₃ ,
438 mL of an aqueous solution containing 141 g and KBr of 102.6
458 mL of an aqueous solution containing g was added by the double jet method so that the final flow rate was 4 times the initial flow rate. After cooling to 55 ° C., 240 mL of an aqueous solution containing 7.1 g of AgNO ₃ .
And an aqueous solution containing 6.46 g of KI by the double jet method
Added over minutes. After adding 7.1 g of KBr, sodium benzenethiosulfonate, 4 mg and K ₂ IrC
l ₆ , 0.05 mg was added. 177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and 223 mL of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. It was washed with water and chemically sensitized in the same manner as Em-J.

(Em-L) (Emulsion for Medium-Sensitivity Red-Sensitive Layer) This was prepared in substantially the same manner as Em-K except that the temperature during nucleation was changed to 42 ° C.

(Em-M, N, O) (Emulsion for low-sensitivity red-sensitive layer) It was prepared in substantially the same manner as Em-H or Em-I. However, the chemical sensitization was performed in the same manner as in Em-J.

(Em-P) (Emulsion for high-sensitivity green sensitive layer) [0510] With respect to Em-J, the sensitizing dyes were changed to 15, 16 and 17, and chemical sensitization was optimally carried out to obtain Em-P. It was

Silver halide emulsion thus obtained
Table 1 shows the characteristics of Em-A1, Q1-T1, Em-A2, Q2-T2, and B-P.

[0512]

[Table 1]

The outline of the preparation formulation of the emulsion of the present invention is shown below. A solution in which a coupler is dissolved in ethyl acetate, a high-boiling-point organic solvent, and a surfactant are added to a 10% gelatin solution, and the mixture is emulsified using a homogenizer (Nippon Seiki) to obtain an emulsion. The surfactant is W-1,
Preparation was carried out using W-4 and W-5 alone or in combination.

1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by mass and Tinuvin P.O. as an ultraviolet absorber. Three
26 (manufactured by Ciba-Geigy Ciba-Geigy Co.) and 2 parts by mass are melted, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and subsequently 130 ° C. Transversely stretched 3.3 times at 250 ° C
After heat fixing for 6 seconds, a PEN (polyethylene naphthalate) film having a thickness of 90 μm was obtained. The PEN film contains a blue dye, a magenta dye, and a yellow dye (I-1 described in the publication technique: Japanese Patent No. 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
5) was added in an appropriate amount. Furthermore, the support was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history at 110 ° C. for 48 hours to obtain a support having less curling tendency.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and Soudium α-on each side. Sulfodi-2-
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH
₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² An undercoat liquid was applied (10c
c / m ² , using a bar coater) and an undercoat layer were provided on the high temperature surface side during stretching. Drying was performed at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.).

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer. 3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, and a dispersion of fine particle powder (secondary aggregate particle diameter of about 0.08 μm) is 0. .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
m ² and resorcinol.

3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m ² / G, long axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am ²
/ Kg, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by mass of iron oxide) 0.0
6 g / m ² of diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed by an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H) as a curing agent
₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. As a matting agent, silica particles (0.3 μm) and 3-
Aluminum oxide (0.15 μm) as an abrasive treated and coated with poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) was added in an amount of 10 mg / each.
It was added so as to be m ² . Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveying devices in the drying zone are 115
C). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) was about 0.1, the saturation magnetization moment of the magnetic recording layer was 4.2 Am ² / kg, and the coercive force was 7.3.
It was × 10 ⁴ A / m and the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH
(OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (compound a, 6 mg /
m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b,
9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1 /
In 1), the mixture was melted in 105 ° C., poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature to prepare a dispersion (average particle diameter 0.01 μm) in acetone, and then added. 15 mg / m of aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as an abrasive.
^It was added to be ² . Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveying devices in the drying zone were 115
C). The sliding layer had a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later was 0.12. It had excellent characteristics.

4) Coating of Photosensitive Layer Next, each layer having the following composition was multilayer coated on the side of the back layer obtained above opposite to the indicator to prepare a sample as a color negative photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent (specific compounds are described below, numerical values are given after symbols, and chemical formulas are listed after them) The numbers corresponding to the respective components are the coating amounts expressed in g / m ² units. For silver halide, the coating amount in terms of silver is shown.

[0520]   First layer (first antihalation layer)   Black colloidal silver 0.155   Surface fog of 0.07 μm AgBrI (2) silver 0.01   Gelatin 0.87   ExC-1 0.002   ExC-3 0.002   Cpd-2 0.001   HBS-1 0.004   HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ⁻³ HBS-1 0.074 Solid Disperse Dye ExF -2 0.015 solid disperse dye ExF-3 0.020.

[0522]   Third layer (middle layer)   0.07 μm AgBrI (2) 0.020   ExC-2 0.022   Cpd-1 0.100   HSB-1 0.062   Polyethyl acrylate latex 0.085   Gelatin 0.294.

[0523]   4th layer (low sensitivity red sensitive emulsion layer)   Em-M silver 0.060   Em-N silver 0.105   Em-O silver 0.123   ExC-1 0.109   ExC-3 0.044   ExC-4 0.072   ExC-5 0.011   ExC-6 0.003   ExC-8 0.042   Cpd-2 0.025   Cpd-4 0.025   HBS-1 0.17   Gelatin 0.80.

[0524]   Fifth layer (medium speed red emulsion layer)   Em-K silver 0.32   Em-L silver 0.42   ExC-1 0.14   ExC-2 0.026   ExC-3 0.020   ExC-4 0.12   ExC-5 0.016   ExC-6 0.007   ExC-8 0.009   Cpd-2 0.036   Cpd-4 0.028   HBS-1 0.16   Gelatin 1.18.

[0525]   6th layer (high-sensitivity red-sensitive emulsion layer)   Em-J silver 1.43   ExC-1 0.18   ExC-3 0.07   ExC-6 0.047   ExC-8 0.003   Cpd-2 0.046   Cpd-4 0.077   HBS-1 0.25   HBS-2 0.12   Gelatin 2.12.

[0526]   7th layer (middle layer)   Cpd-1 0.089   Solid disperse dye ExF-4 0.030   HBS-1 0.050   Polyethyl acrylate latex 0.83   Gelatin 0.84.

[0527]   Eighth layer (multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))   Em-E silver 0.760   Cpd-4 0.030   ExM-2 0.096   ExM-3 0.028   ExY-1 0.031   ExG-1 0.006   HBS-1 0.085   HBS-3 0.003   Gelatin 0.58.

[0528]   9th layer (low sensitivity green emulsion layer)   Em-G Silver 0.39   Em-H silver 0.28   Em-I silver 0.35   ExM-2 0.36   ExM-3 0.045   ExG-1 0.005   HBS-1 0.28   HBS-3 0.01   HBS-4 0.27   Gelatin 1.39.

10th layer (medium speed green emulsion layer) Em-F silver 0.20 Em-G silver 0.25 ExC-6 0.009 ExC-8 0.009 ExM-2 0.031 ExM-30 0.029 ExY-1 0.006 ExM-4 0.028 ExG-1 0.005 HBS-1 0.064 HBS-3 2.1x10 ^-3 gelatin 0.44.

[0530]   11th layer (high sensitivity green emulsion layer)   Em-P Silver 1.200   ExC-6 0.004   ExC-8 0.010   ExM-1 0.016   ExM-3 0.036   ExM-4 0.020   ExM-5 0.004   ExY-5 0.008   ExM-2 0.013   Cpd-4 0.007   HBS-1 0.18   Polyethyl acrylate latex 0.099   Gelatin 1.11.

[0531]   12th layer (yellow filter layer)   Yellow colloidal silver 0.047   Cpd-1 0.16   Solid disperse dye ExF-5 0.010   Solid disperse dye ExF-6 0.010   HBS-1 0.082   Gelatin 1.057.

Thirteenth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Em-B silver 0.18 Em-C silver 0.20 Em-D silver 0.07 ExC-1 0.041 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ⁻³ HBS-1 0.24 Gelatin 1.41.

14th layer (high-sensitivity blue-sensitive emulsion layer) Em-A1 silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0. 075 Cpd-3 1.0x10 ^-3 HBS-1 0.10 gelatin 0.91.

Fifteenth layer (first protective layer) 0.07 μm AgBrI (2) silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F- 18 0.009 F-19 0.005 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.15 B-30 .05 S-1 0.20 W-1 0.025 W-2 5.0 × 10 ^-3 gelatin 0.75.

[0536] Further, each layer is appropriately preserved, processed, pressure resistant, antifungal / antibacterial, B-4 to B-6, F-1 to F-18, and iron salts, lead salts, and gold salts. , Platinum salt, palladium salt, iridium salt, ruthenium salt, rhodium salt are contained. Further, the coating solution for the eighth layer was 8.5 × 10 ⁻³ g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 1.
0 ^-3 grams of calcium was added at calcium nitrate solution, to prepare a sample.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 mL and 5% aqueous solution of p-octylphenoxyethoxyethoxyethoxyethane sulfonate sodium 3 mL and 5
% Aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) into a 700 mL pot mill, 5.0 g of dye ExF-3 and 500 mL of zirconium oxide beads (diameter 1 mm) were added. Was dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, take out the contents,
The mixture was 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 dye fine particles was 0.44 μm.

In the same manner, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.45 μm. E
xF-2 is European Patent Application Publication (EP) No. 549,489.
Microprecipitation (Microp) described in Example 1 of A specification.
It was dispersed by a reciprocation) dispersion method.
The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method. ExF-6 wet cake containing 18% water 2
To 800 g, 4000 g of water and a 3% solution of W-2 37
6 g was added and stirred to obtain a slurry having a concentration of ExF-6 of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultra Visco Mill (UVM-2) manufactured by IMEX Co., Ltd., and a peripheral speed of about 10 was passed through the slurry.
It was pulverized for 8 hours at a discharge rate of 0.5 L / min at m / sec. The compounds used to form each of the above layers are as shown below.

[0540]

[Chemical 98]

[0541]

[Chemical 99]

[0542]

[Chemical 100]

[0543]

[Chemical 101]

[0544]

[Chemical 102]

[0545]

[Chemical 103]

[0546]

[Chemical 104]

[0547]

[Chemical 105]

[0548]

[Chemical formula 106]

[0549]

[Chemical formula 107]

[0550]

[Chemical 108]

[0551]

[Chemical 109]

[0552]

[Chemical 110]

[0553]

[Chemical 111]

The color negative photosensitive material produced as described above is used as sample 101. Emulsion A1 of 14th layer of Sample 101
Samples 102 to 126 in which the antistatic agent W-2 of the 16th layer was changed as shown in Table 2 were similarly prepared. The emulsion was replaced with an equal amount of silver, and the antistatic agent was replaced with an equal amount. 2 at the temperature of 25 ± 1 ° C and relative humidity of 65% ± 5%
The gelatin hardener was allowed to react for a week.

[0555]

[Table 2]

Evaluation of the sample is as follows. It was exposed for 1/100 seconds through a continuous wedge with a gelatin filter SC-39 manufactured by FUJIFILM Corporation (a long wavelength light transmission filter having a cutoff wavelength of 390 nm). Development was carried out by the following using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. Incidentally, the overflow solution of the bleaching bath was modified so that the overflow liquid was discharged into the waste liquid tank without flowing into the post-bath. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992.

The processing steps and processing liquid compositions are shown below. (Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5L Bleach 50 seconds 38.0 ℃ 5 mL 5L Fixing (1) 50 seconds 38.0 ℃ -5L Fixing (2) 50 Sec 38.0 ℃ 8 mL 5L water wash 30 s 38.0 ℃ 17 mL 3L stable (1) 20 s 38.0 ℃ −3L stable (2) 20 s 38.0 ℃ 15 mL 3L dry 1 min 30 s 60.0 ℃ * Replenishment amount is for photosensitive material 35 mm width per 1.1 m (corresponding to 24 Ex. 1 line) The stabilizing solution and the fixing solution were in the countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath (2). The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.5 mL and 2.0 mL per 35 mm width of the photosensitive material, 1.1 m, respectively. It was 2.0 mL. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm ^{2 for the} color developing solution and 120 c for the bleaching solution.
m ² and other treatment liquids were about 100 cm ² .

The composition of the treatment liquid is shown below.   (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3 mg-   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

[0559]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-Diaminopropanetetraacetic acid secondary     Ammonium iron monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with ammonia water] 4.6 4.0   (Fixing (1) Tank liquid)   5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid   (PH 6.8).

[0560]   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas).
120B) and OH type strongly basic anion exchange resin (the same Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / L or less, followed by 20 mg / L sodium diisocyanurate dichloride and 150 mg / L sodium sulfate
Was added. The pH of this liquid was in the range of 6.5 to 7.5.

[0562]   (Stabilizing liquid) Common for tank liquid and replenishing liquid (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average degree of polymerization 10)   1,2-benzisothiazolin-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   1.0L with water added   pH 8.5.

The concentration of the treated sample was measured, and the sensitivity was expressed as a relative value of +0.2. In addition, the fluctuation of processing
The color development process was performed for 3 minutes and 5 seconds and 3 minutes and 35 seconds, and the difference in density of fog was measured.

In the charge adjusting ability test, each sample was processed into a format for the Advanced Photo System, stored in a special cartridge, loaded into the camera, and wound up at high speed in an environment of a temperature of 25 ° C. and a humidity of 10%. After the development processing by the above processing, the fog was visually evaluated.

Table 2 shows the results of the sensitivities of samples 101 to 126, fluctuations in processing fog, and charge controllability. From Table 2, Comparative Compound W-2, when the emulsion of the present invention is used, causes deterioration in processing fog and static fog due to high-speed conveyance by a camera. In addition, comparative compound F which is a short-chain fluorinated alkyl group
C-1 has insufficient charging characteristics even when a comparative emulsion is used. On the other hand, it can be seen that the combination of the emulsion of the present invention and the antistatic compound makes it possible to obtain a light-sensitive material having high sensitivity, small processing fluctuation, and excellent charging characteristics.

(Example 2) Samples 101 to 1 of Example 1
26 was coated on a triacetyl cellulose film support, processed into a 135 format, and evaluated in the same manner as in Example 1. As a result, as in Example 1, the color negative photosensitive material of the present invention showed good results.

(Example 3) First of sample 101 of Example 1
Sample 301 was prepared by performing multilayer coating in the same manner except that the 4th and 16th layers had the following compositions. 14th layer (high-sensitivity blue-sensitive emulsion layer) Em-A2 silver 1.05 ExC-1 0.02 ExY-2 0.41 ExY-3 0.07 ExY-6 0.062 Cpd-2 0.075 Cpd- 3 1.0 × 10 ⁻³ HBS-1 0.13 Gelatin 0.99.

Sixteenth Layer (Second Protective Layer) H-1 0.34 B-1 (diameter 1.7 μm) 5.8 × 10 ⁻² B-2 (diameter 1.7 μm) 0.15 B-30 .05 S-1 0.20 W-1 0.031 W-3 9.5 × 10 ^-3 gelatin 0.60.

Emulsion A2 and 16th of Layer 14 of Sample 301
Sample 302 in which the antistatic agent W-3 of the layer was changed as shown in Table 3
To 325 were similarly prepared. Emulsion is replaced with equal silver amount,
The antistatic agent was changed by equal mass replacement. The sample above
After allowing the gelatin hardening agent to react at a temperature of 25 ° C. ± 1 ° C. and a relative humidity of 65% ± 5% for 2 weeks, the sensitivity, the fog variation of the treatment and the charge adjusting ability were performed in the same manner as in Example 1, and the results are shown in Table 3. Shown in.

[0570]

[Table 3]

From Table 3, Comparative Compound W-3, when the emulsion of the present invention is used, shows deterioration of processing fog and static fog due to high speed conveyance of the camera. Further, the comparative compound FC-2, which is a short-chain fluorinated alkyl group, has insufficient charging characteristics even when the comparative emulsion is used. On the other hand, it can be seen that the combination of the emulsion of the present invention and the antistatic compound makes it possible to obtain a light-sensitive material having high sensitivity, small processing fluctuation, and excellent charging characteristics.

(Example 4) Samples 301 to 3 of Example 3
25 was coated on a triacetyl cellulose film support, processed into a 135 format, and evaluated in the same manner as in Example 3. As a result, as in Example 3, the color negative photosensitive material of the present invention showed good results.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03C 1/85 G03C 1/85 7/392 7/392 Z (72) Inventor Teruichi Yanagi Minamiashigara City, Kanagawa Prefecture 210 Nakanuma Fuji Photo Film Co., Ltd. F term (reference) 2H016 BD00 BD06 BM05 2H023 CA06 CC03 CC04 CC05 CC06 CD00 CD05 FC05 4H006 AA01 AB76 BT12 BU32 BU50 TA04 TB53 TB55

Claims (3)

[Claims] 1. At least one layer of blue each on a support
Sensitive silver halide emulsion layer, green sensitive silver halide emulsion layer,
Silver halide color having a red-sensitive silver halide emulsion layer
In the photographic light-sensitive material, the following general formula (A)
At least one selected from the group of compounds represented by (G)
And a small amount of a compound represented by the following general formula (I):
Silver halide color characterized by containing at least one kind
Photographic material. General formula (A) [Chemical 1] In the ceremony, RED₁₁Represents a reducing group, L₁₁Represents a leaving group
And R₁₁₂Represents a hydrogen atom or a substituent. R₁₁₁Is carbon
Atom (C) and RED₁₁With 5 or 6 members
Tetrahydro form of aromatic ring (including aromatic heterocycle),
Cyclic equivalent to oxahydro or octahydro
Represents a non-metallic atomic group capable of forming a structure. General formula (B) [Chemical 2] In the ceremony, RED₁₂And L₁₂Are each R of the general formula (A)
ED₁₁And L₁₁Represents a group synonymous with. R₁₂₁And R₁₂₂
Is a unit that can be replaced with a hydrogen atom or a carbon atom, respectively.
Represents a substituent, which is R in the general formula (A).₁₁₂Is synonymous with
It ED₁₂Represents an electron-donating group. In general formula (B)
R₁₂₁And RED₁₂, R₁₂₁And R₁₂₂, Or ED₁₂And RE
D₁₂And may be bonded to each other to form a cyclic structure.
Yes. General formula (C) [Chemical 3] In the ceremony, RED₂Is RED of general formula (B)₁₂Group synonymous with
You L₂Represents a carboxy group or a salt thereof, R_{twenty one}, R
_{twenty two}Represents a hydrogen atom or a substituent. RED₂And R_{2 1}What is
They may be bonded to each other to form a ring structure. However, general
The compound represented by the formula (C) has
It is a compound having two or more adsorption promoting groups. General formula (D) [Chemical 4] In the ceremony, RED₃Is RED of general formula (B)₁₂Group synonymous with
You Y₃Is RED₃One electron produced by being oxidized by one electron
Carbon-carbon that can react with oxidants to form new bonds
Reaction containing double bond site or carbon-carbon triple bond site
Represents a sexual group. L ₃Is RED₃And Y₃The linking group that connects and
Represent General formula (E) [Chemical 5] In the ceremony, RED₄₁Is RED of the general formula (B)₁₂A group synonymous with
Represent R₄₀~ R₄₄Are hydrogen atoms or substituents, respectively.
Represent General formula (F) [Chemical 6] In the ceremony, RED₄₂Is RED of the general formula (B)₁₂A group synonymous with
Represent R₄₅~ R₄₉Are hydrogen atoms or substituents, respectively.
Represent Z₄₂Is -CR₄₂₀R₄₂₁-, -NR₄₂₃-Or
Represents -O-. R here₄₂₀, R₄₂₁Is the hydrogen source
Represents a child or a substituent, R₄₂₃Is a hydrogen atom, alkyl
Represents a group, an aryl group, or a heterocyclic group. General formula (G) [Chemical 7] In the ceremony, RED₀Represents a reducing group, L₀Represents a leaving group,
R₀And R₁Represents a hydrogen atom or a substituent. RED₀
And R₀, And R₀And R₁And are linked together to form a ring structure
May be made. General formula (I) [Chemical 8] Where R^{twenty one}Represents a substituted or unsubstituted alkyl group, R
_afRepresents a perfluoroalkylene group. W²Is a hydrogen atom
Or represents a fluorine atom, L_aIs a substituted or unsubstituted
Alkylene group or substituted or unsubstituted alkylene group
A xy group or a divalent group formed by combining these
Represent A²And B²One is a hydrogen atom and the other is
-L_b-SO₃Represents M, and M represents a cation. L_bIs
Represents a single bond or a substituted or unsubstituted alkylene group
You 2. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and at least one layer each on a support.
A silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer contains at least one compound selected from the group of compounds represented by the general formulas (A) to (G), and has the following general formula (II) At least one compound represented by
A silver halide color photographic light-sensitive material containing a seed. General formula (II): In the formula, A ³ and B ³ each independently represent a fluorine atom or a hydrogen atom. a and b each independently represent an integer of 1 to 6. c and d each independently represent an integer of 4 to 8. x represents 0 or 1. M represents a cation. 3. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and at least one layer each on a support.
A silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer contains at least one compound selected from the group of compounds represented by the general formulas (A) to (G), and has the following general formula (III) A silver halide color photographic light-sensitive material comprising at least one compound represented by: General formula (III): In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, but at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom. R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, and
⁴¹ , X ⁴² and Z each independently represent a divalent linking group, and M ⁺ represents a cationic substituent. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1.