JP2005266539A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having high sensitivity, low fog, and excellent storage stability. <P>SOLUTION: The silver halide color photographic sensitive material has on a support one or more each of blue-, green- and red-sensitive silver halide emulsion layers, wherein an emulsion contained in any one of the silver halide emulsion layers has been subjected to reduction sensitization in the presence of a compound represented by formula (I) or (II) (where X and Y each represents sulfo or H with the proviso that at least one of X and Y represents sulfo), and the sensitive material contains a compound selected from type 1: a compound of which one-electron oxidized derivative produced by one electron oxidation of the compound is capable of releasing one or more electrons with a subsequent bond cleavage, and type 2: a compound of which one-electron oxidized derivative produced by one electron oxidation of the compound is capable of releasing one or more electrons after a subsequent bond formation reaction, and a compound represented by formula (B<SB>10</SB>) (where R<SB>b100</SB>-R<SB>b102</SB>each represents H or a substituent; and Z<SB>10</SB>represents a nonmetallic atomic group capable of forming a ring). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material having high sensitivity, low fog and excellent storage stability.

A compound called “one-photon two-electron sensitizer” is known, and its technical contents are described in Patent Documents 1 to 6, for example.
Compounds referred to as “sensitizers capable of emitting one photon and three electrons or more” are disclosed in Patent Documents 7 to 10. With this compound, it is possible to obtain a sensitivity enhancement effect of one photon or two electrons or more, and further advancement of the silver halide color photosensitive material is expected with this sensitivity enhancement as a source.

  Patent Document 11 discloses a technique in which intentional reduction sensitization is performed in the presence of at least one of the sulfodihydroxyaryl compounds represented by the general formulas (I) and (II).

As techniques for increasing the sensitivity of tabular grains, sensitization methods using epitaxial junction are disclosed in Patent Documents 12 and 13. Further, application to tabular grains having a small tabular grain thickness or a larger equivalent circle diameter is disclosed in Patent Documents 14 to 19. In developing “high-sensitivity” photographic materials, it is strongly desired to increase the sensitivity of tabular grains in the future. Patent Document 20 discloses a combined effect of epitaxial sensitization and “one-photon two-electron sensitizer”.
Recently, Patent Document 21 discloses a technique for increasing sensitivity without deteriorating graininess by incorporating a compound having at least three heteroatoms that do not react with an oxidized developing agent into a silver halide photographic material. Has been. Further, Patent Document 22 discloses a further high sensitivity effect by the combined use of the compound of the general formula (M) or the general formula (C) described in the patent document and the “one-photon two-electron emission compound”. ing.
Patent Document 23 discloses a silver halide photographic light-sensitive material that is highly sensitive and excellent in storability by combining a “one-photon two-electron or two-electron emission compound” and a storability improving agent.
US Pat. No. 5,747,235 US Pat. No. 5,747,236 European Patent No. 786692A1 (Compounds INV1 to 35) European Patent No. 893732A1 US Pat. No. 6,054,260 US Pat. No. 5,994,051 JP 2003-114487 A JP 2003-114488 A JP 2003-114486 A JP 2003-140287 A Japanese Patent Laid-Open No. 11-153840 JP 58-108526 A JP 59-133540 A US Pat. No. 5,612,176 US Pat. No. 5,614,359 US Pat. No. 5,629,007 US Pat. No. 5,631,126 US Pat. No. 5,691,127 US Pat. No. 5,726,007 US Pat. No. 6,342,341 JP 2000-194085 A JP 2003-156823 A JP 2003-302719 A

  An object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and low fog and excellent storage stability.

  As a result of intensive studies conducted by the present inventors to solve the problems of the present invention, it has been found that the present invention can be achieved by the following (1) to (6).

(1) 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 each on a support. The silver halide emulsion contained in any of the emulsion layers is subjected to reduction sensitization in the presence of at least one sulfodihydroxyaryl compound represented by the following general formula (I) or (II), and further A silver halide color photographic light-sensitive material comprising a silver color photographic light-sensitive material containing at least one compound selected from the following types 1 and 2 and a compound represented by the general formula (B ₁₀ ):

In general formula (I) and (II), X and Y represent a sulfo group or a hydrogen atom. However, at least one of X and Y represents a sulfo group.
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

In the general formula _{(B 10), R b100,} R b101, R b102 each independently represent a hydrogen atom or a substituent. Z ₁₀ represents a nonmetallic atomic group that can form a ring with —C═CO—.

  (2) 50% or more of the total projected area of the silver halide emulsion grains subjected to reduction sensitization is occupied by silver halide grains satisfying the following (a), (b), and (c): The silver halide color photographic light-sensitive material as defined in (1).

(A) It has a silver halide tabular host grain portion whose main plane is the (111) plane, and (b) at least one epitaxial is bonded to the corner portion of the host grain portion.

(C) When the epitaxial is divided into a portion (A1) projecting outward from the tabular host grain portion and a portion (A2) not projecting when viewed from the direction perpendicular to the main plane of the tabular host grain Further, the average Cl content of epitaxial corresponding to A1 part is 70% or more, and the average Cl content of epitaxial corresponding to A2 part is 60% or less.

  (3) The silver halide color photographic light-sensitive material as described in (1) or (2), which comprises the following compound (A):

Compound (A): a heterocyclic compound having one or more heteroatoms, and a compound which increases the sensitivity of the silver halide color photographic material when added without adding the compound (4) Type 1 Any one of (1) to (3), wherein the compound of type 2 is a compound having in its molecule at least one adsorbing group to silver halide or a partial structure of a spectral sensitizing dye 2. A silver halide color photographic light-sensitive material according to item 1.

  (5) 50% or more of the total projected area of the silver halide emulsion grains subjected to reduction sensitization has a parallel (111) main plane and includes at least 10 dislocation lines per grain. The silver halide color photographic material according to any one of (1) to (4), wherein the silver halide color photographic material is occupied by silver halide grains.

  Hereinafter, the present invention will be described in detail.

  The type 1 and type 2 compounds contained in the silver halide photographic light-sensitive material of the present invention will be described.

(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) shows a compound that can be emitted from a one-electron oxidant produced by one-electron oxidation of a type 1 compound, with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9-211774, JP-A-11-95355 (specific examples: compounds INV1-36), JP-T 2001-500996 (Specific Examples: Compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786662A1 (Specific Examples: Compounds INV1-35), “One-photon two-electron sensitizer” or “deprotonated electron-donating sensitizer” described in patents such as European Patent No. 893732A1, US Pat. No. 6,054,260, US Pat. No. 5,994,051 Compounds referred to. The preferred ranges of these compounds are the same as the preferred ranges described in the detailed documents such as the cited patent applications.

Further, as a compound of type 1 that can be emitted by one-electron oxidant formed by one-electron oxidation and further undergoing bond cleavage reaction, one or more electrons can be emitted from the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) (JP-A-2003-114487) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (synonymous with general formula (3)), general formula (6) (synonymous with general formula (1) described in Japanese Patent Application Laid-Open No. 2003-75950), and general formula (7) (Japanese Patent Application Laid-Open No. 2003-75950). And general formula (8) (Japanese Patent Application No. 2). The reaction represented by the general formula (1) described in 003-25886 or the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446) may occur. Among the compounds, a compound represented by the general formula (9) (synonymous with the general formula (3) described in Japanese Patent Application No. 2003-33446) can be given. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent application specifications.

In the general formulas (1) and (2), RED ₁ and RED ₂ represent a reducing group. R ₁ is a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form or hexahydro form of a 5-membered or 6-membered aromatic ring (including aromatic heterocycle) together with carbon atom (C) and RED ₁ Represent. R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Lv ₁ and Lv ₂ represent a leaving group. ED represents an electron donating group.

In the general formulas (3), (4) and (5), Z ₁ represents an atomic group capable of forming a 6-membered ring together with the nitrogen atom and the two carbon atoms of the benzene ring. _{R 5, R 6, R 7} , R 9, R 10, R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19 represents a hydrogen atom or a substituent. R ₂₀ represents a hydrogen atom or a substituent. When R ₂₀ represents a group other than an aryl group, R ₁₆ and R ₁₇ are bonded to each other to form an aromatic ring or an aromatic heterocycle. R ₈ and R ₁₂ represent a substituent that can be substituted on the benzene ring, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 4. Lv ₃ , Lv ₄ and Lv ₅ represent a leaving group.

In the general formulas (6) and (7), RED ₃ and RED ₄ represent a reducing group. R _{21 to} R ₃₀ represent a hydrogen atom or a substituent. Z ₂ represents —CR ₁₁₁ R ₁₁₂ —, —NR ₁₁₃ —, or —O—. R ₁₁₁ and R ₁₁₂ each independently represents a hydrogen atom or a substituent. _R113 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (8), RED ₅ is a reducing group and represents an arylamino group or a heterocyclic amino group. R ₃₁ represents a hydrogen atom or a substituent. X represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Lv ₆ is a leaving group and represents a carboxy group or a salt thereof, or a hydrogen atom.

The compound represented by the general formula (9) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by further oxidizing after two-electron oxidation accompanied by decarboxylation. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5- or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation. In the general formula (9), R ₃₂ , R ₃₃ and Z ₃ have the same meanings as those in the chemical reaction formula (1). Z ₅ and Z ₆ represent a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group with CC.

Next, the type 2 compound will be described.
As a compound in which a one-electron oxidant produced by one-electron oxidation with a type 2 compound can further emit one or more electrons with a subsequent bond formation reaction, a compound represented by the general formula (10) A compound capable of causing a reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446). And a compound represented by the general formula (11) (synonymous with the general formula (2) described in Japanese Patent Application No. 2003-33446). An organic compound that generates an (n + m) -valent cation with an intramolecular cyclization reaction from an n-valent cation radical described in JP-A-2003-121954 and the like (where n and m are each independently an integer of 1 or more) Are also included in type 2 compounds. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formula (10), RED ₆ represents a reducing group that is one-electron oxidized. Y reacts with one-electron oxidant produced by one-electron oxidation of RED ₆ to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or Reactive group containing a non-aromatic heterocyclic moiety of a benzo-fused ring. Q represents a linking group that links RED ₆ and Y.

The compound represented by the general formula (11) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by being oxidized. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5- or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5-membered aryl group or heterocyclic group with C═C. Z ₅ and Z ₆ represent a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group with C—C. M represents a radical, a radical cation, or a cation. In the general formula (11), R ₃₂ , R ₃₃ , Z ₃ and Z ₄ have the same meanings as in the chemical reaction formula (1).

  Of the compounds of types 1 and 2, “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. Typical examples of the adsorptive group to silver halide are those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  More preferably, the compound of type 1 or 2 is “a compound having at least one adsorptive group to silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferred examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing heterocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing As the quaternary salt structure of phosphorus, a phosphonio group (trialkylphosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) is used. Can be mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.
A preferred structure of the compound represented by types 1 and 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

In general formula (X), P and R each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group, specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR _N —, —C (═O ) —, —SO ₂ —, —SO—, —P (═O) — each independently or a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S is a residue obtained by removing one atom from a compound represented by type (1) or (2). i and j are integers of 1 or more, and are selected from a range in which i + j is 2 to 6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (X) preferably has a total carbon number in the range of 10 to 100. More preferably, it is 10-70, More preferably, it is 11-60, Most preferably, it is 12-50.

Specific examples of the compounds represented by type 1 and type 2 are listed below, but the present invention is not limited thereto.

  The type 1 and type 2 compounds of the present invention may be used at any time during the preparation of the emulsion and during the photosensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

  The compounds of type 1 and type 2 of the present invention are preferably added after being dissolved 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 increased or decreased may be dissolved at a higher or lower pH and added.

The type 1 and type 2 compounds of the present invention are preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 mol per 1 mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-3 mol in a silver halide emulsion layer.

In the present invention, a compound represented by the general formula (B ₁₀ ) is used. When in the formula _{(B 10) R b100, R} b101, R b102 represents a substituent, preferable examples of substituents are chlorine atom, an acylamino group, a ureido group, a sulfonamido group, an alkyl group, an alkylthio group, an alkoxy group An acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, an alkylsulfonyl group, an arylsulfonyl group, and the like. Of these, an alkyl group (particularly a methyl group) is preferred. The ring structure formed by Z ₁₀ is preferably a 5- to 7-membered ring, and a benzene ring or the like may be condensed, and particularly preferably a chroman ring or a 2,3-dihydrobenzofuran ring. These ring structures may have a substituent and may form a spiro ring.

Specific examples of the compound represented by the general formula (B ₁₀ ) are listed below, but the present invention is not limited thereto.

In the present invention, one compound may be selected and used from the compounds represented by formula (B ₁₀ ) of the present invention, but it is also preferable to select and use two or more compounds at the same time. . In this case, any two or more compounds can be selected from the compound represented by the general formula (B ₁₀ ) of the present invention. At this time, the compound represented by the general formula (B ₁₀ ) of the present invention is selected. If classified into (i) those having an adsorptive group, (ii) those having a ballast group, and (iii) those having neither of these, two or three kinds of compounds are selected from these three categories. This is also one of preferred uses of the compound represented by the general formula (B ₁₀ ) of the present invention. When two or more kinds of compounds are used, they may be added in the same layer or in different layers, and the addition method may be different.

Among the compounds represented by the general formula (B ₁₀ ) of the present invention, those having (i) an adsorptive group are added to the same silver halide emulsion layer to which the compound of type 1 or 2 of the present invention is added. It is preferable to add at the time of emulsion preparation. When added at the time of emulsion preparation, it can be added at any time during the process. For example, silver halide grain formation process, before the start of desalting process, desalting process, chemical ripening Examples include a step before starting, a chemical ripening step, and a step before preparing a finished emulsion. Moreover, it can also be added in several steps in these processes. Although it is preferably used in the emulsion layer, it may be added to the adjacent protective layer or intermediate layer together with the emulsion layer and diffused during coating.
The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but is generally 1 × 10 ^{−8 to} 5 × 10 ⁻² mol, more preferably 1 × 10 6 per mol of photosensitive silver halide. ^-7 to 1x10 ^-3 mol.

Among the compounds represented by the general formula (B ₁₀ ) of the present invention, (iii) a diffusible reducing compound is added to the same silver halide emulsion layer as that of the type 1 or 2 compound of the present invention. It can also be added to other non-photosensitive layers. Although it is preferably used in the emulsion layer, it may be added to the adjacent protective layer or intermediate layer together with the emulsion layer and diffused during coating. Although it can be added before chemical ripening, during chemical ripening or after completion of chemical ripening at the time of emulsion preparation, it is preferably added before or during coating of the coating solution.
The preferred amount depends largely on the type of compound to adding method described above or generally per 1 mol of photosensitive silver ^{halide, 5 × 10 -6 ~5 × 10} -2 mol, more preferably 1 × 10 ^{- 5} to 1 × 10 ⁻² mol.

Among the compounds represented by the general formula (B ₁₀ ) of the present invention, those having (ii) a ballast group are added to the same silver halide emulsion layer to which the compound of type 1 or 2 of the present invention is added. It can also be added to other non-photosensitive layers. Although it is preferably used in the emulsion layer, it may be added to the adjacent protective layer or intermediate layer together with the emulsion layer and diffused during coating. Although it may be added at the time of emulsion preparation, it is more preferable to add it at the final stage of emulsion preparation by emulsion dispersion.
The preferred amount depends largely on the type of compound to adding method described above or generally per 1 mol of photosensitive silver ^{halide, 5 × 10 -5 ~5 × 10} -1 mol, more preferably 1 × 10 ^{- 3} to 1 × 10 ⁻¹ mol.

The compound represented by the general formula (B ₁₀ ) of the present invention can be added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. At this time, the pH may be appropriately adjusted with an acid or a base, and a surfactant may be allowed to coexist. Furthermore, it can also be dissolved in a high boiling point organic solvent and added as an emulsified dispersion. Further, it may be added as a solid dispersion (microcrystalline dispersion) by a known dispersion method.

Next, the compound (A) of the present invention will be described in detail.
In the present invention, when the compound (A) is a heterocyclic compound having only one or two heteroatoms, it is a compound that does not react with the oxidized developer, and has at least three heteroatoms. In the case of a heterocyclic ring, it is a compound that reacts with an oxidized developer. Each will be described below.

  Hereinafter, the heterocyclic compound having only one or two heteroatoms used in the present invention will be described. A hetero atom means an atom other than a carbon atom or a hydrogen atom. A heterocycle means a cyclic compound having at least one heteroatom. In a “heterocycle having only one or two heteroatoms”, a heteroatom means only the atoms that form part of the heterocyclic ring system, and is located outside the ring system or at least one It does not mean an atom that is separated from the ring system by one non-conjugated single bond or is part of a further substituent of the ring system.

  In the case of polycyclic heterocycles, all ring systems contain only one or two heteroatoms, eg 1,3,4,6-tetraazaindene heteroatoms It is four and is not included.

  Any heterocyclic compound that satisfies these requirements may be used, but preferably a hetero atom is a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, More preferably, they are a nitrogen atom, a sulfur atom, an oxygen atom, and a selenium atom, Especially preferably, they are a nitrogen atom, a sulfur atom, and an oxygen atom, Most preferably, they are a nitrogen atom and a sulfur atom.

  The number of members of the heterocyclic ring may be any, but is preferably a 3- to 8-membered ring, more preferably a 5- to 7-membered ring, and particularly preferably a 5- and 6-membered ring.

  The heterocyclic ring may be saturated or unsaturated, but preferably has at least one unsaturated portion, and more preferably has at least two unsaturated portions. In other words, the heterocyclic ring may be aromatic, pseudo-aromatic, or non-aromatic, but is preferably an aromatic heterocyclic ring or pseudo-aromatic heterocyclic ring.

  Specific examples of these heterocyclic rings include pyrrole ring, thiophene ring, furan ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring. , An indolizine ring, and an indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, quinoxaline ring, isoquinoline ring, carbazole ring, phenanthridine ring, Examples thereof include a phenanthroline ring, an acridine ring, and a pyrrolidine ring, a pyrroline ring, an imidazoline ring in which these are partially or fully saturated.

Examples of typical heterocycles are shown below.

Examples of the heterocyclic ring condensed with a benzene ring include the following.

Examples of the partially or fully saturated heterocyclic ring include the following.

In addition, the following heterocycles are also possible.

  These heterocyclic rings may be substituted or condensed with any substituents as long as they do not violate the definition of “heterocycle having only one or two heteroatoms”. Of W. Moreover, the tertiary nitrogen atom contained in the heterocyclic ring may be substituted to become quaternary nitrogen. It should be noted that any case where another tautomeric structure of a heterocycle can be written is chemically equivalent.

  In the heterocyclic ring having only one or two heteroatoms, it is preferable that the free thiol group (—SH) and the thiocarbonyl group (> C═S) are not substituted.

  Of the above heterocycles, (aa-1) to (aa-4) are preferred. In (aa-2), it is more preferable that the benzene ring is condensed (ab-25).

  The heterocyclic compound having only one or two heteroatoms may or may not react with the oxidized developing agent, but any heterocyclic compound that does not react with the oxidized developing agent is preferably used. it can.

  That is, those that do not significantly cause a chemical reaction or redox reaction (less than 5 to 10%) directly with the oxidized developing agent are preferred, and are not couplers and react with the oxidized developing agent to produce a dye or any other product. The thing which does not produce | generate a thing is preferable.

The heterocyclic compound having only one or two heteroatoms is more preferably a compound represented by the following general formula (XI).

In the general formula (XI), Z ₁ represents a group that forms a heterocycle having only one or two heteroatoms including a nitrogen atom in the formula. X ₁ represents a sulfur atom, an oxygen atom, a nitrogen atom (N (Va)), or a carbon atom (C (Vb) (Vc)). Va, Vb, and Vc represent a hydrogen atom or a substituent. X ₂ has the same meaning as X ₁ . n ₁ is 0, 1, 2, or 3. When n ₁ is 2 or more, X ₂ is repeated but need not be the same. X ₃ represents a sulfur atom, an oxygen atom, or a nitrogen atom. The bond between X ₂ and X ₃ is a single bond or a double bond, and accordingly X ₃ may further have a substituent or a charge.

The heterocyclic compound having only one or two heteroatoms is particularly preferably a compound represented by the following general formula (XII).

In the general formula (XII), Z _1, and X ₁ are as defined in the general formula (I). X ₄ represents a sulfur atom (S (Vd)), an oxygen atom (O (Ve)), or a nitrogen atom (N (Vf) (Vg)). Vd, Ve, Vf, and Vg represent a hydrogen atom, a substituent, or a negative charge. V ₁ and V ₂ represent a hydrogen atom or a substituent.

Hereinafter, general formula (XI) and general formula (XII) will be described in detail.
Preferred examples of the heterocycle formed by Z ₁ include the heterocycles mentioned in the above [Chemical Formula 20] to [Chemical Formula 23], and the same are preferred. Unless these are contrary to the definition of “heterocycle having only one or two heteroatoms”, these may be further substituted with a substituent (for example, W described below) or condensed.

Examples of the substituent represented by W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, Aryl group, heterocyclic group (also called heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonyl amino Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryl Oxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group And boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known substituents.

X ₁ is preferably a sulfur atom, an oxygen atom, or a nitrogen atom, more preferably a sulfur atom or a nitrogen atom, and particularly preferably a sulfur atom. Examples of the substituent represented by Va, Vb, and Vc include the aforementioned W, and the substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. X ₂ is preferably a carbon atom. n ₁ is preferably 0, 1, 2 and more preferably 2. X ₃ is preferably an oxygen atom. X ₃ is depending bond between X ₂ and X ₃ are either double bond is a single bond, the valence changes. For example, when the bond between X ₂ and X ₃ is a double bond and X ₃ is an oxygen atom, X ₃ represents a carbonyl group, the bond between X ₂ and X ₃ is a single bond and X ₃ is an oxygen atom In this case, X ₃ represents, for example, a hydroxy group, an alkoxy group, a negatively charged oxygen atom, or the like.

X ₄ is preferably an oxygen atom. Examples of the substituent represented by Vd, Ve, Vf, and Vg include those represented by the aforementioned W. It is preferable that at least one of Vd, Ve, and Vf and Vg represents a hydrogen atom or a negative charge. Examples of the substituent represented by V ₁ and V ₂ include the aforementioned W. It is preferable that at least one of V ₁ and V ₂ is a substituent other than a hydrogen atom.

  Specific examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom), an alkyl group (having 1 to 60 carbon atoms. For example, methyl, ethyl, propyl, iso-butyl, t-butyl, t-octyl) , 1-ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (2 to 60 carbon atoms, for example, vinyl, allyl, oleyl), cycloalkyl group (5 to 5 carbon atoms) 60. For example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 1-indanyl, cyclododecyl), aryl group (6 to 60 carbon atoms, for example, phenyl, p-tolyl, naphthyl), acylamino group (2 to 2 carbon atoms) 60. For example, acetylamino, n-butanamide, octanoylamino, 2- Hexyldecanamide, 2- (2 ′, 4′-di-t-amylphenoxy) butanamide, benzoylamino, nicotinamide), sulfonamide group (having 1 to 60 carbon atoms, for example, methanesulfonamide, octanesulfonamide, benzenesulfone) Amide), ureido group (2 to 60 carbon atoms, for example, decylaminocarbonylamino, di-n-octylaminocarbonylamino), urethane group (2 to 60 carbon atoms, for example, dodecyloxycarbonylamino, phenoxycarbonylamino, 2 -Ethylhexyloxycarbonylamino), alkoxy group (C1-C60. For example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, methoxyethoxy), aryloxy group (C6-C60. For example, phenoxy, 2,4-di t-amylphenoxy, 4-t-octylphenoxy, naphthoxy), alkylthio group (C1-C60. For example, methylthio, ethylthio, butylthio, hexadecylthio), arylthio group (C6-C60. For example, phenylthio, 4- Todecyloxyphenylthio), acyl group (C1-C60. For example, acetyl, benzoyl, butanoyl, dodecanoyl), sulfonyl group (C1-C60. For example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group , Carbamoyl group (1 to 60 carbon atoms, for example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (0 to 60 carbon atoms, for example, N, N-dimethylsulfamoyl), hydroxy group, sulfo group, carboxyl group, Nitro group, alkylamino group (charcoal Number 1 to 60. For example, methylamino, diethylamino, octylamino, octadecylamino), arylamino group (carbon number 6 to 60. For example, phenylamino, naphthylamino, N-methyl-N-phenylamino), heterocyclic group (carbon number 0 to 60. Preferably, the hetero atom having a ring structure is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably includes a carbon atom in addition to the hetero atom as the ring atom. 8, More preferably, it is 5-6, for example, the group shown by the above-mentioned W), an acyloxy group (carbon 1-60. For example, formyloxy, acetyloxy, myristoyloxy, benzoyloxy) is preferable.

  Among them, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group Includes those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Sulfonyl group, cyano group, carbamoyl group, sulfamoyl group.

  Among these substituents, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group are preferable, and an alkyl group, an alkoxy group, and an aryloxy group are more preferable. Particularly preferred is a branched alkyl group.

  Although there is no restriction | limiting in particular in the sum total of carbon number of these substituents, Preferably it is 8-60, More preferably, it is 10-57, Especially preferably, it is 12-55, Most preferably, it is 16-53.

  The compounds represented by the general formula (XI) and the general formula (XII) are preferably compounds suitable for the fixing methods (1) to (7) described later, and more preferably (1) and (2). Or (3), particularly preferably (1) or (2), and most preferably (1) and (2). That is, a compound having both a specific pKa and a ballast group can be most preferably used.

The compound (A) of the present invention can contain the necessary number of necessary cations or anions when necessary to neutralize the charge of the compound (A) of the present invention. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (for example, p-toluenesulfonate ion, p- Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

  Preferable compounds (A) of the present invention are combinations of the above-mentioned individual preferable ones (particularly, combinations of individual most preferable ones).

Next, among the heterocyclic compounds having only one or two heteroatoms of the present invention described in detail in the description of the best mode for carrying out the invention, particularly preferred specific examples are shown. Of course, the present invention is not limited to these.

As described above, it is preferable that the heterocyclic compound having only one or two heteroatoms of the present invention does not react with the oxidized developer, but examples of the reacting compounds include those of the following general formula.

In general formulas (III-1) to (III-4), R ₁ , R ₂ and R ₃ are each independently an electron withdrawing property having a Hammett's substituent constant σp value of 0.2 or more and 1.0 or less. Represents a group. R ₄ represents a hydrogen atom or a substituent. However, when there are two R ₄ in the formula, they may be the same or different. X ₅ represents a hydrogen atom or a substituent. Examples of R ₁ , R ₂ , R ₃ , R ₄ , and X ₅ include the same as those described later for R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and X _11, and the same are preferable.

Next, a particularly preferable specific example is shown among the compounds that react with the oxidized developer in a heterocyclic compound having only one or two heteroatoms. Of course, the present invention is not limited to these.

As heterocyclic compounds having only one or two heteroatoms, Edward C. Taylor, edited by Arnold Weissberger, “The Chemistry of Heterocyclic Compounds ( The Chemistry of Heterocyclic Compounds-A Series of Monographs, Volumes 1-59, published by John Wiley & Sons, Robert Sea Elderfield ( Hetero atoms among the compounds described in “Heterocyclic Compounds”, Volumes 1-6, published by John C. Elderfield, published by John Wiley & Sons, etc. Heterocyclic compounds having only one or two can be used. In addition, heterocyclic compounds having only one or two heteroatoms can be synthesized based on the methods described therein.
Synthesis Example: Synthesis of (a-18)

  (A) 7.4 g, (b) 13.4 g, 100 ml of acetonitrile (hereinafter, ml is also referred to as “mL”), and 10 ml of dimethylacetamide were stirred at an internal temperature of 10 ° C. or lower under ice cooling to obtain triethylamine 6 1 mL was added dropwise. Further, after stirring for 2 hours at room temperature, 200 mL of ethyl acetate was added to the reaction solution, washed with dilute aqueous NaOH solution, washed with dilute hydrochloric acid, further washed with saturated brine, and the ethyl acetate layer was washed with magnesium sulfate. After drying, the solvent was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent hexane: ethyl acetate = 19: 1) to obtain 16.2 g of (c). (Yield 96%) (c) After stirring 14.8 g, NaOH 2.8 g, ethanol 50 mL, and water 5 mL at room temperature for 2 hours, 200 mL of water was added, washed and separated with hexane, and the hexane layer was removed. The aqueous layer was separated by adding 200 mL of ethyl acetate and dilute hydrochloric acid to remove the aqueous layer, washed and separated with saturated brine, and the ethyl acetate layer was dried over magnesium sulfate and concentrated under reduced pressure until the solvent was 30 mL. . Hexane was added to the concentrate and stirred, and the precipitated crystals were collected by suction filtration and dried to obtain 13.2 g of colorless crystals (a-18). (Yield: 96%) (melting point: 75-77 ° C.).

  The heterocyclic compound having 3 or more heteroatoms used in the present invention will be described. A hetero atom means an atom other than a carbon atom or a hydrogen atom. A heterocycle means a cyclic compound having at least one heteroatom. The heterocyclic ring of the present invention is a heterocyclic compound having 3 or more heteroatoms. In a “heterocycle having 3 or more heteroatoms”, a heteroatom means only an atom that forms part of a heterocyclic ring system, and is located outside the ring system or at least one non-conjugated It does not mean an atom that is separated from the ring system by a single bond or is part of a further substituent of the ring system.

  In the case of a polycyclic heterocycle, those having 3 or more heteroatoms in all ring systems are included in the present invention, for example, 1H-pyrazolo [1,5-b] [1,2,4] triazole The number of heteroatoms is 4 and is included in the heterocyclic ring having 3 or more heteroatoms of the present invention.

  The upper limit of the number of heteroatoms is not particularly limited, but is preferably 10 or less, more preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less.

  Any heterocyclic compound that satisfies these requirements may be used, but preferably a hetero atom is a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, More preferably, they are a nitrogen atom, a sulfur atom, and an oxygen atom, More preferably, they are a nitrogen atom and a sulfur atom, Especially preferably, they are a nitrogen atom.

  The number of members of the heterocyclic ring may be any, but is preferably a 3- to 8-membered ring, more preferably a 5- to 7-membered ring, particularly preferably 5- and 6-membered rings, and most preferably a 5-membered ring. It is.

  The heterocyclic ring may be saturated or unsaturated, but preferably has at least one unsaturated portion, and more preferably has at least two unsaturated portions. In other words, the heterocyclic ring may be aromatic, pseudo-aromatic, or non-aromatic, but is preferably an aromatic heterocyclic ring or pseudo-aromatic heterocyclic ring.

  The heterocyclic ring is preferably a condensed polycyclic heterocyclic ring, particularly preferably a bicyclic heterocyclic ring.

  The heterocyclic compound having 3 or more heteroatoms may or may not react with the oxidized developing agent, but any heterocyclic compound that reacts with the oxidized developing agent can be preferably used.

Particularly preferred as the heterocyclic ring having 3 or more heteroatoms of the present invention is the case where a compound represented by the following general formula (M) or general formula (C) is used.

In general formula (M), R ₁₀₁ represents a hydrogen atom or a substituent. Z ₁₁ represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). . X ₁₁ represents a hydrogen atom or a substituent.

In General Formula (C), Za represents —NH— or —CH (R ₃ ) —, and Zb and Zc each independently represent —C (R ₁₄ ) ═ or —N═. However, if Za is -NH-, at least one of Zb and Zc are -N =, Za is -CH (R ₁₃₎ - in the case of a both Zb and Zc -N = . R ₁₁ , R ₁₂ and R ₁₃ each independently represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more and 1.0 or less. R ₁₄ represents a hydrogen atom or a substituent. However, when two R < ₁₄ > exists in a formula, they may be same or different. X ₁₁ represents a hydrogen atom or a substituent.

Hereinafter, this compound will be described in detail. Of the skeletons represented by the formula (M), preferred skeletons are 1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4. ] Triazole, each represented by formula (M-1) and formula (M-2).

In the formula, R ₁₅ and R ₁₆ represent a substituent, and X ₁₁ represents a hydrogen atom or a substituent.

The substituents R ₁₅ , R ₁₆ and X _{11 in} formula (M-1) or (M-2) will be described in detail.
R ₁₅ represents a halogen atom (for example, chlorine atom, bromine atom, fluorine atom), alkyl group (having 1 to 60 carbon atoms. For example, methyl, ethyl, propyl, iso-butyl, t-butyl, t-octyl, 1-ethylhexyl) , Nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (2 to 60 carbon atoms, for example, vinyl, allyl, oleyl), cycloalkyl group (5 to 60 carbon atoms, for example) Cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 1-indanyl, cyclododecyl), aryl group (6 to 60 carbon atoms, for example, phenyl, p-tolyl, naphthyl), acylamino group (2 to 60 carbon atoms, for example) Acetylamino, n-butanamide, octanoylamino, 2-hexyldecane Amide, 2- (2 ′, 4′-di-t-amylphenoxy) butanamide, benzoylamino, nicotinamide), sulfonamide group (having 1 to 60 carbon atoms. For example, methanesulfonamide, octanesulfonamide, benzenesulfonamide) ), Ureido groups (2 to 60 carbon atoms, such as decylaminocarbonylamino, di-n-octylaminocarbonylamino), urethane groups (2 to 60 carbon atoms, such as dodecyloxycarbonylamino, phenoxycarbonylamino, 2- Ethylhexyloxycarbonylamino), alkoxy group (C1-C60. For example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, methoxyethoxy), aryloxy group (C6-C60. For example, phenoxy, 2 , 4-Di-t-amylpheno Ci, 4-t-octylphenoxy, naphthoxy), alkylthio group (C1-C60. For example, methylthio, ethylthio, butylthio, hexadecylthio), arylthio group (C6-C60. For example, phenylthio, 4-todecyloxy) Phenylthio), acyl group (having 1 to 60 carbon atoms, for example, acetyl, benzoyl, butanoyl, dodecanoyl), sulfonyl group (having 1 to 60 carbon atoms, for example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group, carbamoyl group (C1-C60. For example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (C0-60, for example, N, N-dimethylsulfamoyl), hydroxy group, sulfo group, carboxyl group, nitro group, Alkylamino group (having 1 to 60 carbon atoms). For example, methylamino, diethylamino, octylamino, octadecylamino), arylamino group (carbon number 6 to 60. For example, phenylamino, naphthylamino, N-methyl-N-phenylamino), heterocyclic group (carbon number 0 to 60. Preferably, the hetero atom having a ring structure is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably includes a carbon atom in addition to the hetero atom as the ring atom. 8, more preferably 5-6, for example, the groups exemplified) in the section of X ₁₁ to be described later, an acyloxy group (carbon 1 to 60. for example, formyloxy, acetyloxy, myristoyl, benzoyloxy) are preferred.

  Among them, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group Includes those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Sulfonyl group, cyano group, carbamoyl group, sulfamoyl group.

Of these substituents, preferred R ₁₅ includes an alkyl group, an aryl group, an alkoxy group, and an aryloxy group, and more preferred are an alkyl group, an alkoxy group, and an aryloxy group. Particularly preferred is a branched alkyl group.

R ₁₆ is preferably a substituent exemplified for R ₁₂ , and more preferable substituents are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an aryloxy group.
More preferred are an alkyl group and a substituted aryl group, and the most preferred group is a substituted aryl group, and compounds represented by general formulas (M-3) and (M-4) are preferred.
There is no particular limitation on the total number of carbon atoms of the substituents on the azole ring containing R ₁₀₁ , X ₁₁ , and Z ₁₁ in the general formula (M), but the adsorptivity to emulsion grains is improved, and the sensitivity / granularity ratio is increased. In order to enhance the improvement effect, it is preferably 13 or more and 60 or less, and more preferably 20 or more and 50 or less.

In the formula, R ₁₅ and X ₁₁ are synonymous with the general formulas (M-1) and (M-2), and R ₁₇ represents a substituent. Preferred examples of the substituent for R ₁₇ include the substituents listed above as examples of R ₁₅ . More preferable examples of the substituent include a substituted aryl group and a substituted or unsubstituted alkyl group. In this case, the substituents listed above as examples of R ₁₅ are preferable.

X ₁₁ represents a hydrogen atom or a substituent, and as the substituent, the substituents listed above as examples of R ₁₅ are preferable. More preferably, the substituent for X ₁₁ represents an alkyl group, an alkoxycarbonyl group, a carbamoyl group, or a group that leaves upon reaction with an oxidized form of a developing agent, such as a halogen atom (fluorine, chlorine, bromine, etc.) ), Alkoxy groups (ethoxy, methoxycarbonylmethoxy, carboxypropyloxy, methanesulfonylethoxy, perfluoropropoxy, etc.), aryloxy groups (4-carboxyphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, 4-methanesulfonyl- 3-carboxyphenoxy, 2-methanesulfonyl-4-acetylsulfamoylphenoxy, etc.), acyloxy groups (acetoxy, benzoyloxy, etc.), sulfonyloxy groups (methanesulfonyloxy, benzenesulfonyloxy, etc.), acylamino (Such as heptafluorobutyrylamino), sulfonamide group (such as methanesulfonamide), alkoxycarbonyloxy group (such as ethoxycarbonyloxy), carbamoyloxy group (such as diethylcarbamoyloxy, piperidinocarbonyloxy, morpholinocarbonyloxy), Alkylthio groups (such as 2-carboxyethylthio), arylthio groups (such as 2-octyloxy-5-t-octylphenylthio, 2- (2,4-di-t-amylphenoxy) butyrylaminophenylthio), complex Ring thio group (1-phenyltetrazolylthio, 2-benzimidazolylthio, etc.), heterocyclic oxy group (2-pyridyloxy, 5-nitro-2-pyridyloxy, etc.), 5-membered or 6-membered nitrogen-containing heterocycle Groups (1-triazolyl, 1-imidazolyl, 1-pyrazoli , 5-chloro-1-tetrazolyl, 1-benzotriazolyl, 2-phenylcarbamoyl-1-imidazolyl, 5,5-dimethylhydantoin-3-yl, 1-benzylhydantoin-3-yl, 5,5-dimethyl Oxazolidine-2,4-dione-3-yl, purine and the like) and azo groups (such as 4-methoxyphenylazo and 4-pivaloylaminophenylazo).

Particularly preferred as a substituent for X ₁₁ is an alkyl group, an alkoxycarbonyl group, a carbamoyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, a 5-membered group bonded to the coupling activity with a nitrogen atom, or 6 A nitrogen-containing heterocyclic group, particularly preferably an alkyl group, a carbamoyl group, a halogen atom, a substituted aryloxy group, a substituted arylthio group, an alkylthio group, or a 1-pyrazolyl group.

The compounds represented by the general formulas (M-1) and (M-2) and preferably used in the present invention may form a dimer or higher multimer via R ₁₁ and R _12. Further, it may be bonded to a polymer chain. In the present invention, the general formula (M-1) is preferable, and the general formula (M-3) is more preferable.

Next, general formula (C) will be described. Specifically, the general formula (C) of the present invention is represented by the following general formulas (bc-3) to (bc-6).

Wherein, R ₁₁ to R _14, and X ₁₁ are as defined respectively in formula (C).

  In the present invention, compounds represented by general formulas (bc-3) and (bc-4) are preferable, and a compound represented by (bc-3) is particularly preferable.

In the general formula (C), the substituent represented by R ₁₁ , R ₁₂ and R ₁₃ is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σp value of 0.2 or more and 0.8 or less. Hammett's rule was established in 1935 by L.L. to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb advocated by Hammet, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values are described in many general books. A. Dean ed. "Lange's Handbook of Chemistry" 12th edition, 1979 (McGaw-Hill) and "Chemical area special edition", 122, 96-103, 1979 (Nanedo) Chemical Review, 91, 165-195 Page, detailed in 1991.

In the present invention, R ₁₁ , R _12, and R ₁₃ are defined by Hammett's substituent constant values, but they do not mean that they are limited only to substituents having known values described in these documents. Of course, even if the value is unknown, it is included as long as it is included in the range when measured based on the Hammett rule.

Specific examples of electron withdrawing groups having a σp value of 0.2 or more and 1.0 or less include acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, cyano groups, nitro groups, dialkylphosphono groups, diarylphosphones Group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, and the like. Among these substituents, the group that can further have a substituent may further have a substituent as described in R ₄ described later.

R ₁₁ , R ₁₂ and R ₁₃ are preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group or a sulfonyl group, and more preferably a cyano group, an acyl group, an alkoxycarbonyl group or an aryl group. An oxycarbonyl group and a carbamoyl group.

The combination of R ₁₁ and R ₁₂ is preferably when R ₁₁ is a cyano group and R ₁₂ is an alkoxycarbonyl group.

R ₁₄ represents a hydrogen atom or a substituent, and examples of the substituent include the substituents listed in R ₁₅ above.

Preferred substituents for R ₁₄ include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, and acylamino groups. More preferred are alkyl groups and substituted aryl groups, and the most preferred groups are , A substituted aryl group. Examples of the substituent in this case include the substituents listed above.
X ₁₁ is the same as X ₁₁ in formula (M).
Specific examples of those which react with the oxidized developing agent among the heterocyclic compounds having 3 or more heteroatoms preferably used in the present invention are shown below, but the present invention is not limited thereto.

  The compound (A) of the present invention is prepared according to the synthesis method described in, for example, JP-A-61-65245, JP-A-61-65246, JP-A-61-147254, JP-A-8-122984, and the like. Easy to synthesize.

  As described above, the heterocyclic compound having 3 or more heteroatoms in the present invention preferably reacts with an oxidized developing agent, but a heterocyclic compound that does not react with the oxidized developing agent can also be used. These will be described below.

Specific examples of these heterocyclic rings include triazole ring, oxadiazole ring, thiadiazole ring, benzotriazole ring, tetraazaindene ring, pentaazaindene ring, purine ring, tetrazole ring, pyrazolotriazole ring and the like.
Examples of typical heterocycles are shown below.

Examples of the 6/5 bicyclic heterocyclic compound of the present invention include a tetraazaindene ring, a pentaazaindene ring, and a hexaazaindene ring.

Numbering the position of the nitrogen atom according to the structure above, (1,3,4,6) and (1,3,5,7) (known as purines) as tetraazaindene rings , (1, 3, 5, 6), (1, 2, 3a, 5), (1, 2, 3a, 6), (1, 2, 3a, 7), (1, 3, 3a, 7) , (1,2,4,6), (1,2,4,7), (1,2,5,6) and (1,2,5,7) can be used. These compounds can also be expressed as derivatives of imidazo-, pyrazolo-, or triazolo-pyrimidine rings, pyridazine rings, or pyrazine rings. As the pentaazaindene ring, (1, 2, 3a, 4, 7), (1, 2, 3a, 5, 7), (1, 3, 3a, 5, 7) and the like can be used. As the hexaazaindene ring, (1, 2, 3a, 4, 6, 7) or the like can be used. More preferably, 1,3,4,6-tetraazaindene ring, 1,2,5,7-tetraazaindene ring, 1,2,4,6-tetraazaindene ring, 1,2,3a, 7- They are a tetraazaindene ring and a 1,3,3a, 7-tetraazaindene ring.
Specific preferred examples are shown below.

In the case of these tetraazaindene rings, pentaazaindene rings, and hexaazaindene rings, an ionizable substituent such as a hydroxy group, a thiol group, a primary amino group, or a secondary amino group is ring-attached to the ring atom. Preferred are cases where they are not joined so that they can be conjugated to nitrogen to form heterocyclic tautomers.
In addition, the following heterocycles are mentioned.

  A heterocyclic ring in which part or all of the above heterocyclic ring is saturated may be used, but as described above, it is preferably not saturated.

  These heterocyclic rings may be substituted or condensed with any substituent unless the definition of “heterocycle having 3 or more heteroatoms” is contrary to the above. Can be mentioned. Moreover, the tertiary nitrogen atom contained in the heterocyclic ring may be substituted to become quaternary nitrogen. It should be noted that any case where another tautomeric structure of a heterocycle can be written is chemically equivalent.

In the heterocyclic ring of the present invention, it is preferable that the free thiol group (—SH) and the thiocarbonyl group (> C═S) are not substituted.
Of the above heterocycles, (ca-1) to (ca-11) are preferred.

  The heterocyclic compounds mentioned here are compounds that do not react with the oxidized developing agent. That is, those that do not significantly cause a chemical reaction or redox reaction (less than 5 to 10%) directly with the oxidized developing agent are preferred, and are not couplers and react with the oxidized developing agent to produce a dye or any other product. The thing which does not produce | generate a thing is preferable.

Next, specific examples of heterocyclic compounds having 3 or more heteroatoms that do not react with the oxidized developing agent will be shown. Of course, the present invention is not limited to these.

  As the compound (A) of the present invention, in addition to the specific examples described above, compounds corresponding to the present invention described in the specific examples of JP-A No. 2000-194085 can be preferably used.

  As the compound (A) of the present invention, Edward C. Taylor, edited by Arnold Weissberger, “The Chemistry of Heterocyclic Compounds” -A Series of Monographs, Volumes 1-59, published by John Wiley & Sons, edited by Robert C. Elderfield Among the compounds described in “Heterocyclic Compounds” Vols. 1-6, published by John Wiley & Sons, etc. Can do. Moreover, the compound (A) of this invention is compoundable based on the method as described in these.

  As the substituent of the compound (A) of the present invention described above, any substituent for obtaining desired photographic characteristics for a specific application used by those skilled in the art can be selected. They include, for example, hydrophobic groups (ballast groups), solubilizing groups, blocking groups, releasable or releasable groups. In general, these groups preferably have 1 to 60, more preferably 1 to 50 carbon atoms.

  In order to control the movement of the compound (A) of the present invention in the light-sensitive material, the molecule may contain a high molecular weight hydrophobic group or ballast group or a polymer main chain.

  The carbon number in a typical ballast group is preferably 8 to 60, more preferably 10 to 57, particularly preferably 12 to 55, and most preferably 16 to 53. As these substituents, substituted or unsubstituted C 8-60, preferably 10-57, more preferably 13-55, particularly preferably 16-53, most preferably 20-50 alkyl, aryl groups, Or a heterocyclic group is mentioned. Moreover, it is preferable that these contain a branch. Typical substituents on these groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl , Alkylsulfonyl, arylsulfonyl, sulfonamido, and sulfamoyl groups, the substituents generally having 1 to 42 carbon atoms. For example, W mentioned above is mentioned. Moreover, such a substituent may be further substituted.

  The ballast group will be described in more detail. Specifically, an alkyl group (having 1 to 60 carbon atoms, for example, methyl, ethyl, propyl, iso-butyl, t-butyl, t-octyl, 1-ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (carbon number 2 to 60. For example, vinyl, allyl, oleyl), cycloalkyl group (carbon number 5 to 60. For example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 1- Indanyl, cyclododecyl), aryl group (C6-C60. For example, phenyl, p-tolyl, naphthyl), acylamino group (C2-C60. For example, acetylamino, n-butanamide, octanoylamino, 2- Hexyldecanamide, 2- (2 ′, 4′-di-t-amylphenoxy ) Butanamide, benzoylamino, nicotinamide), sulfonamide group (C1-C60. For example, methanesulfonamide, octanesulfonamide, benzenesulfonamide), ureido group (C2-C60. For example, decylaminocarbonylamino) , Di-n-octylaminocarbonylamino), urethane group (2 to 60 carbon atoms, for example, dodecyloxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), alkoxy group (1 to 60 carbon atoms, for example, Methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, methoxyethoxy), aryloxy group (6 to 60 carbon atoms. For example, phenoxy, 2,4-di-t-amylphenoxy, 4-t-octylphenoxy, Naphthoxy) , Alkylthio groups (having 1 to 60 carbon atoms, such as methylthio, ethylthio, butylthio, hexadecylthio), arylthio groups (having 6 to 60 carbon atoms, such as phenylthio, 4-todecyloxyphenylthio), acyl groups (having 1 to 1 carbon atoms). 60. For example, acetyl, benzoyl, butanoyl, dodecanoyl), sulfonyl group (C1-C60. For example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group, carbamoyl group (C1-C60. For example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (0 to 60 carbon atoms, for example, N, N-dimethylsulfamoyl), hydroxy group, sulfo group, carboxyl group, nitro group, alkylamino group (1 to 60 carbon atoms, for example). , Methylamino, diethylamino, octylami , Octadecyl amino), arylamino group (having 1 to 60 carbon atoms. For example, phenylamino, naphthylamino, N-methyl-N-phenylamino), heterocyclic group (0 to 60 carbon atoms, preferably selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom of the ring structure Further, those containing a carbon atom in addition to a hetero atom as a ring-constituting atom are further preferred, and the number of ring members is 3 to 8, more preferably 5 to 6, for example, the group represented by the aforementioned W), an acyloxy group (Carbon 1-60. For example, formyloxy, acetyloxy, myristoyloxy, benzoyloxy) is preferable.

  Among them, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group Includes those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Sulfonyl group, cyano group, carbamoyl group, sulfamoyl group, and halogen atom.

  Among these substituents, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group are preferable, and an alkyl group, an alkoxy group, and an aryloxy group are more preferable. Particularly preferred is a branched alkyl group.

  Although there is no restriction | limiting in particular in the sum total of carbon number of these substituents, Preferably it is 8-60, More preferably, it is 10-57, Especially preferably, it is 12-55, Most preferably, it is 16-53.

  When the compound (A) of the present invention is contained in a silver halide photographic light-sensitive material, it is preferable that the silver halide photographic light-sensitive material can be fixed to a specific layer at the time of storage, and at an appropriate time of photographic processing (preferably during development processing) This is the case where a diffusing compound is used. In order to prevent and fix the diffusion of the compound (A) of the present invention during storage, any compound / method may be used, but the following compounds / methods are preferable.

  (1) A method in which a compound having a specific pKa is added after being emulsified and dispersed together with a high-boiling organic solvent, which will be described later, so that the compound (A) of the present invention is dissociated and eluted from the oil only during development.

  The pKa of the compound (A) of the present invention is preferably 5.5 or more, more preferably 6.0 to 10.0, particularly preferably 6.5 to 8.4, most preferably 6. .9 or more and 8.3 or less.

The dissociation group may be any group, but is preferably a carboxyl group, —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ —. Group (sulfonylsulfamoyl group), sulfonamido group, sulfamoyl group, phenolic hydroxyl group, and more preferably carboxyl group, —CONHSO ₂ — group, —CONHCO— group, —SO ₂ NHSO ₂ — group, Particularly preferred are a carboxyl group and a —CONHSO ₂ — group.

  (2) A method in which a ballast group is added to the compound (A) of the present invention to make it diffusion resistant.

  (3) A method using a blocking group. Compounds that change properties (eg, become diffusible) by chemical reactions such as nucleophilic reactions, electrophilic reactions, oxidation reactions, reduction reactions, etc. in the photographic processing process can be used. You can also use the method.

  As an example, the nucleophilic reaction will be described in detail. The nucleophilic reaction can occur under any conditions, but is promoted by a base or by heating, particularly in the presence of a base. As the base, any base can be selected from inorganic bases and organic bases. For example, tertiary amines such as triethylamine, aromatic heterocyclic amines such as pyridine, OH anions such as sodium hydroxide and potassium hydroxide. Bases having In particular, in the present invention, the nucleophilic reaction is promoted by photographic processing having a high pH, such as a developer, among photographic processing, so that it can be preferably used.

  The term “nucleophile” as used herein refers to an atom having a low electron density, such as carbonyl carbon, contained in a group of atoms that form a group that is eliminated when attacked by a nucleophile to give or share electrons. Represents a chemical species with properties. The nucleophile may have any structure, but preferred examples include reagents that give hydroxide ions (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate), sulfite ions (For example, sodium sulfite, potassium sulfite), a hydroxylamide ion (for example, hydroxyamine), a hydrazide ion (for example, hydrazine hydrate, dialkylhydrazines), a hexacyanoferrate (II) ion And a reagent (eg, sodium methoxide) that gives a reagent (eg, yellow blood salt), cyanide ion, tin (II) ion, ammonia, or alkoxy ion. Examples of groups capable of leaving upon attack by a nucleophile include Can. J. et al. Chem. 44, 2315 (1966), JP-A-59-137,945, JP-A-60-41,034, and the like. Lett. 585 (1988), JP-A-59-218,439, JP-B-5-78,025, etc., a group using a nucleophilic reaction, a group using a hydrolysis reaction of an ester bond or an amide bond, etc. Can be mentioned.

  In order to impart the above function, the compound (A) of the present invention may be substituted with a blocking group that releases the compound (A) of the present invention during the photographic processing. A well-known thing can be used as a blocking group. For example, the acyl groups described in JP-B-48-9968, JP-A-52-8828, JP-A-57-82834, U.S. Pat. No. 3,311,476 and JP-B-47-44805 (U.S. Pat. No. 3,615,617). , Blocking groups such as sulfonyl groups, Japanese Patent Publication Nos. 55-17369 (US Pat. No. 3,888,677), 55-9696 (US Pat. No. 3,791,830), 55-34927 (US Pat. No. 4,009,029), JP No. 56-77842 (US Pat. No. 4,307,175), No. 59-105640, No. 59-105641 and No. 59-105642, etc. U.S. Pat.Nos. 3,674,478, 3,932,480, 3,993,661, JP-A-57-135944, 57-135945 (U.S. Pat. No. 4,420,554), 57-136640, 61-196239, Quinones by intramolecular electron transfer described in 61-196240 (US Pat. No. 4,702,999), 61-185743, 61-124941 (US Pat. No. 4,639,408) and JP-A-2-280140 Blocking group utilizing the formation of a compound similar to tide or quinone methide, U.S. Pat. Nos. 4,358,525, 4,330,617, JP 55-53330 (U.S. Pat. No. 4,310,612), 59-121328, 59-218439 No. 63-318555 (European Published Patent No. 0295729) and the like, a blocking group utilizing an intramolecular nucleophilic substitution reaction, JP-A 57-76541 (US Pat. No. 4,335,200), 57- 135949 (US Pat. No. 4,350,752), 57-179842, 59-137945, 59-140445, 59-219741, 59-202459, 60-41034 (US Pat. No. 4,618,563) No. 62-59945 (U.S. Pat. No. 4,888,268), 62-65039 (U.S. Pat. No. 4,772,537), 62-80647, JP-A-3-236047 and 3-238445, etc. Blocking groups utilizing a 5- or 6-membered ring cleavage reaction, JP-A-59-201057 (US Pat. No. 4,518,685), 61-43739 (US Pat. No. 4,659,651), 61 -95346 U.S. Pat. No. 4,690,885), 61-95347 (U.S. Pat. No. 4,892,811), JP-A Nos. 64-7035 and 4-42650 (U.S. Pat. No. 5,066,573), JP-A No. 1-245255, No. 2 No. 207249, 2-235055 (US Pat. No. 5,118,596) and 4-186344, etc., and a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond, -93442, 61-32839, 62-163051, and the blocking group utilizing β-elimination reaction described in JP-B-5-37299, etc., described in JP-A-61-188540 Blocking group utilizing nucleophilic substitution reaction of diarylmethanes, Blocking group utilizing Rossen rearrangement described in JP-A-62-187850, JP-A-62-80646, JP-A-62-144163, and JP-A-62 -Block group utilizing reaction of N-acyl thiazolidine-2-thione with amines described in JP-A No. 147457, JP-A-2-296240 (US Pat. No. 5,019,492), 4-177243, 4-177244, 4-177245, 4-177246, 4-177247, 4-177248, 4-177248, 4-177249, 4-177948, 4 -184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419, JP-A-5-45816, etc. Examples thereof include blocking groups that react with nucleophiles, and JP-A-3-236047 and JP-A-3-238445. Of these blocking groups, JP-A-2-296240 (US Pat. No. 5,019,492), 4-177243, 4-177244, 4-177245, 4-177246, 4-177246, 4-177247, 4-177248, 4-177249, 4-179748, 4-184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 And a blocking group that reacts with a dinucleophile having two electrophilic groups described in JP-A-5-45816 and the like. These blocking groups may be groups containing a timing group that causes a cleavage reaction using an electron transfer reaction described in U.S. Pat.Nos. 4,409,323 or 4,421,845. It is preferable that the terminal which causes an electron transfer reaction is blocked.

  (4) A method using a dimer containing a partial structure of the compound (A) of the present invention, or a polymer compound of a trimer or higher.

(5) A method of fixing using the compound (A) (solid dispersion) of the present invention which is insoluble in water. As described in (1), it is preferable that the compound (A) of the present invention has a specific pKa because the compound (A) of the present invention dissolves only during development. Examples using water-insoluble dye solids (solid dispersions) are disclosed in JP-A Nos. 56-12539, 55-155350, 55-155351, 63-27838, 63-197943, and Europe. This is disclosed in Japanese Patent No. 15,601.
A detailed method for solid dispersion will be described later.

  (6) A method of immobilizing the compound (A) of the present invention by coexisting a polymer having a charge opposite to that of the compound (A) of the present invention as a mordant. Examples of fixing the dye are disclosed in U.S. Pat. Nos. 2,548,564, 4,124,386, and 3,625,694.

  (7) A method of immobilizing the compound (A) of the present invention by adsorbing it on a metal salt such as silver halide. Examples of fixing the dye are disclosed in US Pat. Nos. 2,719,088, 2,496,841, 2,496,843, and JP-A-60-45237.

  Typical examples of the adsorbing group to silver halide that can be used in the compound (A) of the present invention include groups described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. Is something.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferable examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing terocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  Further, a quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkyl phosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) Is mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

  Among these, the method for fixing the compound (A) of the present invention is preferably (1) a method using a compound having a specific pKa, (2) a method using a compound having a ballast group, and (3) a blocking group. (5) a method using a solid dispersion, and it is preferable to use a compound suitable for these. More preferred is the method / compound of (1), (2) or (3), and particularly preferred is the method / compound of (1) or (2). Most preferably, the methods (1) and (2) are used at the same time, that is, the compound (A) of the present invention having a specific pKa and a ballast group can be most preferably used.

The compound (A) of the present invention can contain the necessary number of necessary cations or anions when necessary to neutralize the charge of the compound (A) of the present invention. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (for example, p-toluenesulfonate ion, p- Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

  Preferable compounds (A) of the present invention are combinations of the aforementioned individual preferable ones (particularly, combinations of the individual most preferable ones).

  In addition, when the compound (A) of the present invention has a plurality of asymmetric carbons in the molecule, there are a plurality of stereoisomers for the same structure, but in this specification all possible stereoisomers. In the present invention, only one of a plurality of stereoisomers can be used, or several of them can be used as a mixture.

  The compound (A) of the present invention may be used alone or in combination of two or more, and the number and type of compounds used can be arbitrarily selected.

  Further, the compound (A) of the present invention may be used in combination with a compound having at least 3 heteroatoms described in JP-A No. 2000-194085 and JP-A No. 2003-156823.

  The compound (A) of the present invention can be used in combination with one or a plurality of methods having a high sensitivity effect or a compound having a high sensitivity effect. Also in this case, the method used and the number and types of the compounds to be contained can be arbitrarily selected.

In the present invention, it is sufficient that the compound of the present invention can act on a silver halide photographic light-sensitive material (preferably a silver halide color photographic light-sensitive material). It may be used for any non-photosensitive layer.
When used for a silver halide photosensitive layer, when the photosensitive layer is divided into a plurality of layers having different sensitivities, it may be used for any sensitive layer, but is preferably used for the most sensitive layer.
When used for the non-photosensitive layer, it is preferably used for the non-photosensitive layer located between the red-sensitive layer and the green-sensitive layer or between the green-sensitive layer and the blue-sensitive layer. The non-photosensitive layer means all layers other than the silver halide emulsion layer, and examples thereof include an antihalation layer, an intermediate layer, a yellow filter layer, and a protective layer.

  The method of adding the compound of the present invention to the light-sensitive material is not particularly specified, but the method of adding by emulsifying and dispersing together with a high boiling point organic solvent, the method of adding by dispersing solid, the method of adding to the coating solution in the form of a solution (For example, it is added by dissolving in an organic solvent such as water or methanol, or a mixed solvent), and a method of adding at the time of preparing a silver halide emulsion. However, it can be introduced into a light-sensitive material by emulsion dispersion and solid dispersion. Preferably, it is a case where it introduce | transduces into a sensitive material by emulsification dispersion | distribution.

  As the emulsification dispersion method, an oil-in-water dispersion method in which it is dissolved in a high boiling point organic solvent (a low boiling point organic solvent can be used in combination), emulsified and dispersed in an aqueous gelatin solution and added to the silver halide emulsion is used.

  Examples of high boiling point organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the latex dispersion method as one of the polymer dispersion methods include US Patent No. 4,199,363, West German Patent (OLS) No. 2,541,274, Japanese Patent Publication No. 53-41091, and European Patent Application Publication. Nos. 0,727,703 and 0,727,704 and the like. Further, a dispersion method using an organic solvent-soluble polymer is described in WO88 / 723.

  Examples of the high-boiling organic solvent that can be used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate), phosphoric acid or phosphonic acid esters ( For example, triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, fatty acid esters (eg, di-2-ethylhexyl succinate, tributyl citrate), benzoic acid esters (eg, benzoic acid) 2-ethylhexyl, dodecyl benzoate, etc.), amides (eg, N, N-diethyldodecanamide, N, N-dimethyloleinamide, etc.), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-) tert-amylphenol), anilines (for example, N, N-dibuty) 2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins, hydrocarbons (eg, dodecylbenzene, diisopropylnaphthalene, etc.), carboxylic acids (eg, 2- (2,4-di-tert-amyl) Phenoxy) butyric acid, etc.). Further, an organic solvent having a boiling point of 30 ° C. or higher and 160 ° C. or lower (for example, ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methyl cellosolve acetate, dimethylformamide, etc.) may be used in combination as an auxiliary solvent. The high boiling point organic solvent is preferably used in an amount of 0 to 10 times, preferably 0 to 4 times the mass ratio of the compound of the present invention.

  From the viewpoint of improving stability over time during storage in the emulsion dispersion state, suppressing photographic performance changes in the final coating composition mixed with emulsion, and improving stability over time, the emulsion dispersion may be reduced in pressure as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation, washing with noodles or ultrafiltration.

  The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (trade name, Coulter Electronics).

  Further, as the solid fine particle dispersion method, the powder of the compound of the present invention is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, a vibration ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves, and the solid dispersion is obtained. The method of producing is mentioned. At that time, a protective colloid (for example, polyvinyl alcohol) and a surfactant (for example, an anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three isopropyl groups having different substitution positions)) are used. Also good. In the mills, beads such as zirconia are usually used as a dispersion medium, and Zr and the like eluted from these beads may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of 1 to 1000 ppm. If the content of Zr in the light-sensitive material is 0.5 mg or less per 1 g of silver, there is no practical problem. The aqueous dispersion can contain a preservative (eg, benzoisothiazolinone sodium salt).

  In the present invention, for the purpose of obtaining a solid dispersion having a high S / N, a small particle size, and no aggregation, a dispersion method in which an aqueous dispersion is converted into a high-speed flow and then subjected to pressure drop can be used. As for the solid dispersion apparatus and its technology used for carrying out such a dispersion method, for example, “Dispersion Rheology and Dispersion Technology” (Toshio Kajiuchi, Hiroki Arai, 1991, Shinyamasha Publishing Co., Ltd.) p.357 to p403), “Progress of Chemical Engineering Vol. 24” (Chemical Engineering Society, Tokai Branch, 1990, Tsuji Shoten, p.184 to p185).

The addition amount of the compounds of the present invention is preferably from 0.1 to 1000 mg / m ^2, more preferably ^{1~500mg / m 2, 5~100mg / m} 2 is particularly preferred. When used in a light-sensitive silver halide emulsion layer, 1 × 10 ⁻⁵ to 1 mol is preferable, 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol is more preferable, and 1 × 10 10 per mol of silver in the same layer. ^{−3 to} 5 × 10 ⁻² mol is particularly preferred. Two or more compounds of the present invention may be used in combination. In this case, those compounds may be added to the same layer or to another layer.

  The pKa of the compound of the present invention is determined by the following method. Add 0.5 mL of 1N sodium chloride to 100 mL of a 6: 4 (mass ratio) tetrahydrofuran / water solution in which 0.01 mmol of the compound of the present invention is dissolved (hereinafter, mL is also referred to as “mL”). The solution is titrated with a 0.5N aqueous potassium hydroxide solution while stirring under a nitrogen gas atmosphere. The pH at the center of the inflection point of the titration curve with the horizontal axis representing the dropping amount of the aqueous potassium hydroxide solution and the vertical axis representing the pH value was defined as pKa. In the case of a compound having a plurality of dissociation sites, there are a plurality of inflection points, and a plurality of pKa values can be obtained. The inflection point can also be determined by monitoring the ultraviolet / visible absorption spectrum and examining the change in absorption.

  In general, the photographic speed is determined by the size of the silver halide emulsion grains. The larger the emulsion grains, the more the photographic speed increases. However, since the graininess deteriorates with an increase in the size of silver halide grains, sensitivity and graininess are in a trade-off relationship.

  In addition to increasing the size of the silver halide emulsion grains described above, sensitivity can be increased by methods such as increasing the activation of couplers and reducing the amount of development inhibitor releasing couplers (DIR couplers). Although it is possible, when the sensitivity is increased by these methods, the graininess is deteriorated at the same time. These methods, such as emulsion grain size change, coupler activity adjustment, and DIR coupler quantity adjustment, are intended to deteriorate graininess while increasing sensitivity in the trade-off relationship between sensitivity and graininess. Or it is only an “adjustment means” for improving the graininess while reducing the sensitivity.

The present invention is not a method for increasing sensitivity with granular deterioration commensurate with sensitivity increase.
The present invention provides a method for increasing sensitivity without accompanying deterioration in graininess, or a method for increasing sensitivity, in which the increase in sensitivity is large compared to deterioration in graininess. In the present invention, when an increase in sensitivity and a deterioration in graininess occur at the same time, the sensitivity is compared after combining the graininess using the “adjusting means”, and a substantial increase in sensitivity is observed.

  A substantial increase in sensitivity is defined as a sensitivity difference of 0.02 or more when the photosensitive material is exposed through a continuous wedge and the sensitivity is compared with the logarithm of the reciprocal of the exposure amount giving the minimum density +0.5.

  The halogen composition of the silver halide emulsion of the present invention is preferably silver chlorobromide or silver iodochlorobromide.

  In the present invention, the silver iodide content in the silver halide emulsion is preferably 2 mol% or more and 25 mol% or less, more preferably 5 mol% or more and 20 mol% or less with respect to the total silver amount in the grain. The silver chloride content is preferably 1 mol% or more and 20 mol% or less, more preferably 2 mol% or more and 10 mol% or less, based on the total silver amount in the grain.

  In the emulsion of the present invention, the relative standard deviation of the silver iodide content distribution between grains is preferably 20% or less. More preferably, it is 10% or less. The relative standard deviation of the silver iodide content between grains can be easily determined by using the EPMA method (Electron-Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared and irradiated with an electron beam. Elemental analysis of a very small portion can be performed by X-ray analysis by electron beam excitation. Using this method, the halogen composition of individual grains can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the halogen composition is confirmed by the EPMA method for at least 100 grains, it can be determined whether or not the emulsion is an emulsion according to the present invention. The relative standard deviation of silver iodide content is a value obtained by dividing the standard deviation of the distribution of silver iodide content for at least 100 grains by the average silver iodide content and multiplying by 100.

  The emulsion of the present invention preferably has a relative standard deviation of the silver chloride content distribution between grains of 20% or less. More preferably, it is 10% or less. The measurement method is the same as that described above.

  The emulsion of the present invention is preferably monodisperse. The variation coefficient of the equivalent sphere diameter of all the silver halide grains constituting the emulsion of the present invention is preferably 30% or less, more preferably 25% or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The coefficient of variation is a value obtained by dividing the standard deviation of the distribution of equivalent diameters of individual silver halide grains by the average equivalent diameter.

  In the silver halide emulsion of the present invention, at least 50% of the total projected area of silver halide grains contained is a tabular host grain portion and at least one or more epitaxial junctions at the corner portion of the tabular host grain portion. Preferably, the silver halide grains are occupied.

  First, the tabular host grain portion will be described. In the present invention, a tabular host grain portion (hereinafter also referred to as “tabular grain” or “host grain”) refers to a silver halide grain having two opposing parallel (111) major planes. The tabular grain of the present invention has one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points are mirror images on both sides of the (111) plane.

The silver halide emulsion reduced and sensitized in the presence of the sulfodihydroxyaryl compound represented by the general formula (I) or (II) contained in the silver halide color photographic light-sensitive material of the present invention is the above requirement (a). It is preferable to satisfy (c). The use layer of the silver halide emulsion satisfying the above requirements (a) to (c) is represented by the layer containing the compound represented by the above type 1 or 2 and / or the general formula (B ₁₀ ). Although it may be different from the layer containing the compound, it is preferable to use the same layer.

  Furthermore, the silver halide emulsion satisfying the above requirements (a) to (c) can be used in any color sensitive emulsion layer of the silver halide color photographic light-sensitive material of the present invention. In the case where the chromatic layer is composed of a plurality of layers having different sensitivities, it can be used in any of the high sensitivity layer, medium sensitivity layer and low sensitivity layer. The silver halide emulsion satisfying the above requirements (a) to (c) is preferably used in the high-sensitivity blue-sensitive layer for achieving the effects of the present invention.

  The tabular grains have a triangular shape, a hexagonal shape, or a round shape in which they are round when the grains are viewed from the vertical direction from the main plane, and have outer surfaces parallel to each other.

  In the tabular grains of the present invention, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 preferably occupy 100 to 50% of the total number of grains. More preferably 100 to 70%, still more preferably 100 to 80%. In the emulsion of the present invention, more preferably hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 occupy 100 to 50% of the total number of grains. More preferably, it accounts for 100 to 70%, particularly preferably 100 to 80%.

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

  As for the projected area diameter and thickness of the tabular grains, the diameter (projected area diameter) and thickness of a circle having an area equal to the projected area of each grain are obtained by taking a transmission electron micrograph by the replica method. In this case, the thickness is calculated from the length of the shadow of the replica.

  The tabular grains preferably have a projected area diameter of 2.0 to 20.0 μm, more preferably 3.0 to 10.0 μm. The equivalent sphere diameter is preferably 0.6 μm or more and 5.0 μm or less, and more preferably 1.0 μm or more and 4 μm or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The aspect ratio is preferably 8 or more and 100 or less, more preferably 10 or more and 50 or less. The aspect ratio is a value obtained by dividing the projected area diameter of a grain by the thickness of the grain.

  The variation coefficient of the projected area diameter of the tabular grains is preferably 35% or less, and more preferably 30% or less. Further, the variation coefficient of the thickness of the tabular grain is preferably 30% or less, and more preferably 25% or less. The coefficient of variation is a value obtained by dividing the standard deviation of the distribution of equivalent diameters of individual silver halide grains by the average equivalent diameter, or a value obtained by dividing the standard deviation of thickness distribution of individual silver halide tabular grains by the average thickness. It is.

  Further, the variation coefficient of twin plane spacing distribution of all tabular grains of the emulsion of the present invention is preferably 25 to 3%, more preferably 20 to 3%, still more preferably 15 to 3%. The variation coefficient of the twin plane spacing distribution is a value obtained by dividing the thickness variation (standard deviation) of the twin plane spacing of each tabular grain by the average twin plane spacing. If the variation coefficient of the twin plane spacing distribution of all tabular grains exceeds 25%, it is not preferable in terms of homogeneity between grains. Also, it is difficult to prepare an emulsion of less than 3%.

  In the present invention, the silver iodide content in the silver halide tabular grains is preferably 2 mol% or more and 25 mol% or less, more preferably 5 mol% or more and 20 mol% or less with respect to the total silver amount in the grains. The silver chloride content is preferably 0.5 mol% or more and 10 mol% or less with respect to the total silver amount in the grain.

  In the silver halide tabular grains in the present invention, the (100) plane area with respect to the average side area determined from the average projected area diameter and average thickness of all grains is preferably 10% or more with respect to the side area. . Specifically, 20% or more and 100% or less is more preferable, and 30% or more and 80% or less is more preferable. The side surface refers to a portion sandwiched between two parallel main planes, and the average projected area diameter and average thickness of all particles are measured by transmission electron micrograph photography by the replica method described above. Can be sought. The method described in T. Tani et al J. Img. Sci, 29 165-171 (1985) can be used for the crystal plane of the tabular grain. Specifically, the ratio of the (100) plane to the (111) plane is obtained by this method, and the ratio of the (100) plane can be obtained from this ratio.

  The silver halide tabular grains contained in the emulsion of the present invention preferably have a so-called core / shell structure composed of a core part having different silver iodide contents and a shell surrounding the core part. . The shell part may surround the entire core part, may surround only the side surfaces of the tabular grains of the core part, or may surround only the main flat surface part. The number of shells may be one or two or more. When the number of shells is two or more, the shell outside the core is called the first shell, the shell outside the first shell is called the second shell, and the shells outside the following are called the third shell and the fourth shell in order. . In this specification, “outermost layer” refers to the outermost shell.

The core part is preferably 30% or more and 50% or less, and more preferably 40% or more and 60% or less, based on the total amount of silver used for grain formation. The average content of iodine with respect to the amount of silver in the core may be basically 0 mol% or more and below the solid solution limit, but more preferably 1 mol% or more and 25 mol% or less.
The shell portion may be divided into several layers as described above. The average iodine content of each layer of the shell part is preferably 1 mol% or more and the solid solution limit or less, and more preferably 2 mol% or more and 20 mol% or less.

  The iodine content (I1) of the tabular grain main plane and the iodine content (I2) of the tabular grain side surface may be (i) I1 = I2, (ii) I1> I2, or (iii) I1 <I2. . The relationships (i) to (iii) can be designed according to the purpose. I1 and I2 refer to the iodine content of the silver halide phase 5 nm deep from the surface.

  Examples of the method for measuring the iodine content include the following methods. The tabular grain is cut into a ring perpendicular to the main plane and measured by irradiating an electron beam from the cross-sectional direction. That is, the emulsion sampled during grain formation, the final grain emulsion after grain formation, or the grains taken out from the photosensitive material by centrifugation are coated on a triacetylcellulose support, and the resin is used to wrap the grains. Buried. An about 50 nm-thick section is cut from this sample with an ultramicrotome and placed on a copper mesh with a support film.

  A predetermined portion of the grain is subjected to a point analysis with a spot diameter (diameter) reduced to 2 nm or less using an analytical electron microscope to measure the silver iodide content. The silver iodide content can be calculated by treating silver halide grains having a known content as a calibration curve in the same manner and obtaining the ratio of Ag intensity to I intensity in advance. A field emission electron gun with a higher electron density than the one using thermoelectrons is suitable as the analytical electron source for the analytical electron microscope. By narrowing the spot diameter to 1 nm or less, the halogen composition in a minute part can be easily analyzed. it can. The measured values of I1 and I2 of the individual silver halide grains are measured at 10 or more locations at regular intervals for the main plane portion and the side portion, and the average value is used.

  The core part preferably does not contain dislocation lines, and the shell part may not contain dislocation lines, but preferably contains 10 or more dislocation lines per grain.

Next, the epitaxial will be described.
In a preferred silver halide emulsion of the present invention, a silver halide grain having a total projected area of 50% or more has a silver halide tabular host grain portion and at least one epitaxial junction at the corner of the host grain portion. doing. Epitaxial bonding is that the crystal | crystallization which protruded outside is joined to the tabular grain surface. The composition of the epitaxial portion may be the same as that of the silver halide tabular grains, but is preferably not the same. Specific examples include AgBr, AgCl, AgI, AgBrI, AgClI, AgBrCl, AgBrClI, AgSCN and the like, and AgBrCl and AgBrClI are preferable. The corner of the tabular grain is preferable for the epitaxial junction position. The corner portion means a portion where a circle and a tabular grain overlap each other when a circle having a radius r is written from the apex portion of the apex triangle or hexagon when the tabular grain is viewed from the vertical direction. Here, r is the length of y% of the length connecting the center and vertex of the tabular grain, and y is 2% or more and 50% or less, preferably 5% or more and 30% or less.
The number of epitaxials may be present at at least one apex, and may be present at a plurality of apexes.

  As shown in FIG. 1, the epitaxial layer according to the present invention is divided into an epitaxial portion corresponding to a portion (A1 portion) that protrudes outside the tabular grain and a portion (A2 portion) that does not protrude when viewed from the direction perpendicular to the main plane of the tabular grain. Has a corresponding epitaxial. The epitaxial corresponding to the A1 portion and the epitaxial corresponding to the A2 portion are in contact with each other to form one epitaxial. The present invention is characterized in that the epitaxial composition differs between the epitaxial corresponding to the A1 part and the epitaxial corresponding to the A2 part.

  The average Cl content of A1 part is preferably 70% or more, more preferably 80% or more (including 100%). The average Cl content of the A2 part is preferably 60% or less (including 0%), more preferably 50% or less. Here, the average Cl content of A1 part and the average Cl content of A2 part are the average Cl content in epitaxial corresponding to A1 part in one epitaxial and the average Cl content in epitaxial corresponding to A2 part, respectively. The content rate.

  The halogen composition of the epitaxial part is examined by analytical electron microscopy. In the present invention, tabular grains are sliced perpendicularly to the main plane by the following method, and measurement is performed by irradiating an electron beam from the cross-sectional direction. That is, the emulsion sampled during grain formation, the final grain emulsion after grain formation, or the grains taken out from the photosensitive material by centrifugation are coated on a triacetyl cellulose support, and the resin is used to wrap the grains. Buried. An about 50 nm-thick section is cut from this sample with an ultramicrotome and placed on a copper mesh with a support film.

  The silver chloride content is measured by performing point analysis on a predetermined portion of the grain using an analytical electron microscope with a spot diameter (diameter) reduced to 2 nm or less. The silver chloride content can be calculated by treating silver halide grains having a known content as a calibration curve in the same manner and obtaining the ratio of Ag intensity to Cl intensity in advance. A field emission electron gun with a higher electron density than the one using thermoelectrons is suitable as the analytical electron source for the analytical electron microscope. By narrowing the spot diameter to 1 nm or less, the halogen composition in a minute part can be easily analyzed. it can.

  With respect to the epitaxial shape, {100} plane, {111} plane, and {110} plane may appear on the epitaxial surface, or a plurality thereof may appear. Further, it may have an irregular shape in which a higher-order surface appears.

  The amount of silver in the epitaxial portion (when there are a plurality of epitaxial layers) is the total amount of silver in one grain, that is, the total amount of silver in the silver halide tabular host grains and the amount of epitaxial silver, It is preferably 3% or more and 50% or less, and more preferably 5% or more and 30% or less.

  The amount of silver in the epitaxial portion can also be estimated from an electron micrograph. In that case, the silver amount of the epitaxial part can be obtained by first multiplying the area of the epitaxial part when viewed from the main plane direction of the grain by the thickness of the epitaxial part when viewed from the grain cross-sectional direction. The amount of silver in the host particle portion can be determined by multiplying the area of the host particle portion when viewed from the main plane direction of the particle by the thickness of the host particle portion when viewed from the particle cross-sectional direction.

  The observation from the grain cross-sectional direction can be carried out from the grain side face direction by cutting the tabular grains perpendicularly to the main plane by the following method. That is, the emulsion grains are sampled during grain formation, and gelatin is removed by centrifugation. Then, the grains are coated on a triacetyl cellulose support, and the grains are embedded using a resin. A section having a thickness of about 50 nm is cut from this sample with an ultramicrotome and placed on a copper mesh provided with a support film, and observed using a transmission electron microscope.

  Alternatively, a method may be used in which the amount of silver is estimated by dissolving the particles with a solvent using the difference in solubility due to the difference in halogen composition between the epitaxial portion and the host particle portion. In that case, first dissolve the higher part of the epitaxial part or the host particle part with a weak solvent, measure the amount of silver by atomic absorption, etc., then dissolve the remaining part with a solvent and measure the amount of silver. Can be obtained.

  Below, the preparation method of a silver halide grain is demonstrated. As a method for preparing a silver halide emulsion, a method in which after forming silver halide nuclei and further growing silver halide grains to obtain grains of a desired size, the present invention is also the same. There is no change. The tabular grain formation includes at least nucleation, ripening, and growth steps. This process is described in detail in US Pat. No. 4,945,037. The growth step is a step of growing silver halide grain nuclei by adding a silver salt aqueous solution and a halogen salt solution to a reaction vessel by a double jet method. A method of controlling pAg in the reaction solution in the growth by the double jet method can also be used.

Next, the method for preparing the silver halide emulsion of the present invention will be described in detail.
The preparation step of the present invention includes a core portion forming step ((a) step), a shell portion forming step ((b) step), and an epitaxial forming step ((c) step). Basically, it is preferable to perform all the steps (a), (b), and (c), but the step (b) may not be provided.

  First, step (a), which is a step of forming the core portion, will be described. The core part formation process can be manufactured through processes well known in the art, that is, a process of nucleation process-aging process-growth process. Hereinafter, nucleation, ripening, growth, and each process will be described.

1. Nucleation Step Tabular grain nucleation is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of a protective colloid, or a protective colloid solution containing an alkali halide. A single jet method is used in which a silver salt aqueous solution is added. Moreover, the method of adding aqueous alkali halide solution to the protective colloid solution containing a silver salt as needed can also be used. Furthermore, if necessary, a protective colloid solution, a silver salt solution, and an alkali halide aqueous solution are added to a mixer disclosed in JP-A-2-44335, and immediately transferred to a reaction vessel, whereby the core of tabular grains is obtained. Formation can also be performed. 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. .

  Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide, etc. (methionine content 40 μmol / g or less), amino group-modified gelatin (eg, phthalated gelatin, trimellitized) Gelatin, succinylated gelatin, maleated gelatin, esterified gelatin), and low molecular weight gelatin (weight average molecular weight: 3000 to 40,000) are used. Japanese Patent Publication No. 5-12696 can be referred to for the oxidized gelatin, and Japanese Patent Application Laid-Open Nos. 8-82883 and 11-143002 can be referred to for the amino group-modified gelatin. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are described in Japanese Patent Publication No. 7-111550, Research Disclosure Magazine Vol. 176, No. 17643 (December 1978), section IX.

In nucleation, it is usually preferred that an excess of halogen salt is present before and / or during nucleation. In this case, the excess halogen salt is preferably Cl ⁻ , Br ⁻ , or I ⁻ , and these may be used alone or in plural. In the present invention, Cl ^- it is preferred that there exists. The total halogen salt concentration is preferably 3 × 10 ⁻⁵ mol / liter or more and 0.1 mol / liter or less, more preferably 3 × 10 ⁻⁴ mol / liter or more and 0.01 mol / liter or less.

The halogen composition in the halide solution added at the time of nucleation is preferably Br ⁻ , Cl ⁻ , or I ⁻ , and these may be used alone or in plural. In the present invention, Cl ^- there is preferred to, this time that the composition of the Cl in the silver halide nuclei after nucleation is preferably at least 5 mol% 100 mol% or less, still more than 10 mol% 80 mol% or less preferable.

  The protective colloid may be dissolved in an aqueous alkali halide solution added at the time of nucleation. The temperature during nucleation is preferably from 5 to 60 ° C, but more preferably from 5 to 48 ° C when producing fine tabular grains having an average particle size of 0.5 µm or less. The pH of the dispersion medium is preferably 4 or more and 8 or less when amino group-modified gelatin is used, but preferably 2 or more and 8 or less when other gelatin is used.

2. Aging process In the nucleation, fine particles other than tabular grains (especially octahedral and single twin grains) are formed. Before entering the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. In order to make this possible, it is well known to perform Ostwald ripening following nucleation.

  Immediately after nucleation, pBr is adjusted, and then the temperature is increased and ripening is performed until the hexagonal tabular grain ratio reaches the maximum. At this time, a protective colloid solution may be additionally added. In this case, the concentration of the protective colloid with respect to the dispersion medium solution is preferably 10% by mass or less. As the additional protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, low molecular weight gelatin, natural polymer, or synthetic polymer is used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used.

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

At this time, a silver halide solvent may be added so that grains other than the tabular grains disappear quickly. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / liter or less, and more preferably 0.2 mol / liter or less.
Thus, it is aged so as to be almost 100% tabular grains only.

After the ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows.
(i) In the case of an alkaline silver halide solvent such as NH ₃ , an acid having a large solubility product with Ag ⁺ such as HNO ₃ is added to be invalidated.
(ii) In the case of a thioether-based silver halide solvent, it is invalidated 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, completion of the ripening step means grains other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes (regular and single twin grains). ) Refers to the time when it disappears. The disappearance of grains other than tabular grains having a principal plane of hexagonal or triangular shape 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, an over-aging step described in JP-A-11-174606 may be provided as necessary. The over-ripening step is a step of erasing tabular grains having a low anisotropic growth speed by further aging the tabular grains themselves after ripening (ripening step) until the hexagonal tabular grain ratio reaches the maximum. 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, and more preferably to 60 or more and 80 or less by the over-ripening step.

  In the method for producing an emulsion of the present invention, conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. In the overripening step, a silver halide solvent can be added in the same manner as in the ripening step, and the type, concentration, etc. can be set to be the same as those in the ripening step.

3. Growth Process It is preferable to keep pBr in the crystal growth period following the ripening process at 1.4 to 3.5. When the concentration of the protective colloid in the dispersion medium solution before entering the growth process is low (1% by mass or less), the protective colloid may be additionally added. In addition, protective colloids may be added during the growth process. The timing 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, oxidized gelatin, natural polymer, or synthetic polymer is used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. The pH during growth is preferably 4 to 8 or less when amino group-modified gelatin is present, and 2 to 8 is preferable otherwise. The addition rate of Ag ⁺ and halogen ions in the crystal growth period is preferably 20 to 100%, preferably 30 to 100% of the crystal critical growth rate. In this case, the addition rate of silver ions and halogen ions is increased with crystal growth. In this case, the addition rate of silver salt and halogen salt aqueous solution as described in Japanese Patent Publication Nos. 48-36890 and 52-16364. The concentration of the aqueous solution may be increased.

  When performing the double jet method in which a silver salt aqueous solution and a halogen salt aqueous solution are added simultaneously, in order to prevent the introduction of growth dislocation due to heterogeneous iodine, it is possible to improve the stirring of the reaction vessel and dilute the concentration of the added solution. preferable.

  A method of adding the AgI fine grain emulsion prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution is more preferable, and it is preferable that at least 50% or more of the total silver amount is grown by this method. 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. The AgI fine grain emulsion to be added may be prepared in advance or may be added while continuously preparing. JP-A-10-43570 can be referred to for the preparation method in this case.

  The average grain size of the added AgI emulsion is 0.01 μm or more and 0.1 μm or less, preferably 0.02 μm or more and 0.08 μm or less. The iodine composition of the base grains can be changed depending on the amount of AgI emulsion to be added.

Further, silver iodobromide fine particles may be added in place of the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, the base particles having a desired iodine composition can be obtained by making the iodine amount of the fine particles equal to the iodine amount of the desired base particles. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while preparing them continuously outside the reaction vessel. JP-A-10-43570 can be referred to for the preparation method. The size of the silver iodobromide fine particles to be added is 0.005 μm or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less. The temperature during growth is 60 ° C. or higher and 90 ° C. or lower, preferably 70 ° C. or higher and 85 ° C. or lower.
Furthermore, the above ion addition method, AgI fine particle addition method, and AgBrI fine particle addition method may be combined.

Next, the process (b) which is a shell part is demonstrated.
The shell part may surround the entire core part, may surround only the side surfaces of the tabular grains of the core part, or may surround only the main flat surface part. The number of shells may be one or two or more. When the number of shells is two or more, the shell outside the core is called the first shell, the shell outside the first shell is called the second shell, and the shells outside the following are called the third shell and the fourth shell in order. . In this specification, “outermost layer” refers to the outermost shell.

The shell part may be divided into several layers as described above. The average iodine content of each layer of the shell part is preferably 1 mol% or more and the solid solution limit or less, and more preferably 2 mol% or more and 20 mol% or less.
However, the average iodine content of the shell part immediately before the outermost layer may be 20 mol% or more and 100 mol% or less.

  In this case, as is apparent from the average silver iodide content, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal during shell formation. In either case, normally, silver iodide disappears and all changes to a silver iodobromide mixed crystal upon formation of the next outermost shell.

  For the growth of the shell, 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.

Further, there is a method in which silver iodobromide or silver iodide fine grain emulsion is added and ripened and dissolved. Further, as a preferred method, there is a method of adding a silver iodide fine grain emulsion and then adding a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halogen aqueous solution. Further, by using the iodide ion releasing agent described in US Pat. No. 5,496,694, a silver halide phase containing silver iodide can be formed while abruptly generating iodide ions.
Any of the above methods may be used, or a combination thereof may be used.

  The silver iodobromide fine grain emulsion may be prepared in advance as described above, but it is preferable to add it while preparing it continuously outside the reaction vessel. JP-A-10-43570 can be referred to for the preparation method. The size of the silver iodobromide fine particles to be added is 0.005 μm or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less.

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. 100% silver iodide is preferred. Silver iodide may preferably have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in its crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before the addition described in US Pat. No. 5,004,679 or the like, or may be one that has undergone a normal water washing step. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the grain size is preferably 0.1 μm or less, more preferably 0. 0.07 μm or less.

  The silver iodobromide fine grain emulsion and the silver iodide fine grain emulsion are preferably added continuously during the shell formation. However, in the case of the shell formation immediately before the outermost layer, the silver iodide fine grain emulsion may be added rapidly. preferable.

  With respect to iodide ion release, for example, JP-B-7-11549, JP-A-5-341418, JP-A-5-346631, JP-A-5-323487, JP-A-6-11780, JP-A-6-11781, and JP-A-6-11787. No. 6-11784, 6-27564, 6-138595, 6-230495, 6-242527, 6-250309, 6-250310, 6-250311, 6-250313, 6-258745, 6-273766, 6-313933, 7-219102, 8-62754, 8-95181, U.S. Pat.No. 5,389,508, 5,418,124, 5,482,826, 5,496,694, 5,498,516, 5,580,713, 5, It is preferable to use a method of releasing iodide ions from the iodide ion-releasing agent by reaction with an alkali or a nucleophilic agent according to 27,664 No. or the like. Regarding the iodide ion releasing agent, it is preferable to use the specific compounds and the usage thereof described in the above patent application.

  (B) Although dislocation lines do not have to exist in the part of the step, it is more preferable that they exist. The dislocation lines are preferably present in the vicinity of the edge portion or the corner portion of the tabular grain. The vicinity of the edge part means the outer peripheral part (edge part) of six sides of the tabular grain and the inner part thereof. As described above, the vicinity of the corner is surrounded by the perpendicular and its side when a perpendicular is drawn from the point of x% from the center of the straight line connecting the center of the particle and each vertex to the side that creates each vertex. It is a three-dimensional part. The value of x is preferably 50 or more and less than 100, more preferably 75 or more and less than 100. The average number of dislocation lines present at the edge or corner is preferably 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

  The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, the silver halide hexagonal tabular grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% of the projected area of all grains, more preferably 100 to 70%, especially Preferably it occupies 100 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  Next, the epitaxial bonding process which is the process (c) will be described. Regarding the epitaxial formation of silver halide on tabular grains, as described in US Pat. No. 4,435,501, iodide ions adsorbed on the surface of tabular grains, aminoazaindene, spectral sensitizing dyes, etc. It is shown that the silver salt epitaxial layer can be formed at a site where the silver salt epitaxial layer is selected, for example, at a side surface portion or a corner portion of a tabular grain. JP-A-8-69069 achieves high sensitization by forming silver salt epitaxials at selected sites of an ultrathin tabular grain base and optimally sensitizing this epitaxial phase.

  In the present invention, the tabular grains are sensitized in the same way as in these methods, but in the present invention, the epitaxial portion is a portion protruding from the tabular grains when viewed from the direction perpendicular to the main plane of the tabular grains. And an epitaxial composition protruding from the tabular grains when viewed from the direction perpendicular to the tabular grain main plane, the tabular grain main plane, and the protruding portion. This is characterized in that it differs from the epitaxial portion bonded to both of them, thereby achieving further higher sensitivity.

  In the present invention, an amino site indene or spectral sensitizing dye may be used as the epitaxial site director, or iodide ion or thiocyanate ion may be used. These can be used properly or combined according to the purpose.

  By changing the amount of sensitizing dye, iodide ion, and thiocyanate ion, the silver salt epitaxial formation site can be limited to the main plane, side, or corner of the tabular grain. A combination thereof is also possible. The addition amount of aminoazaindene, iodide ion, thiocyanate ion and spectral sensitizing dye used in the site director should be appropriately selected according to the silver amount, surface area, and epitaxial limited site of the silver halide tabular grain used. Is preferred. The temperature for forming the silver salt epitaxial is preferably 30 to 70 ° C, and more preferably 35 to 60 ° C. In this case, the pAg is preferably 9.0 or less, and more preferably 8.0 or less. The pH is preferably from 3.0 to 8.0, more preferably from 4.0 to 7.0. In this way, by selecting the type, addition amount, and epitaxial deposition conditions (temperature, pAg, pH, etc.) of the site director as appropriate, it is possible to select silver salt epitaxial for the main plane, side, or corner of the tabular grain. Can be formed.

  After the addition of the site director, the silver salt aqueous solution and the halogen salt aqueous solution may be added simultaneously for epitaxial formation, but the silver salt aqueous solution may be added after the halogen salt aqueous solution is added. Further, after adding the halogen salt aqueous solution, the silver salt aqueous solution and the halogen salt aqueous solution may be added simultaneously.

  The epitaxial formation may be performed several times by changing the pAg and pH during the epitaxial formation, or may be performed several times by changing the halogen salt composition. In particular, it is preferable to perform the epitaxial formation in several steps by changing the halogen composition.

  When epitaxially changing the halogen composition, the silver salt aqueous solution and the halogen salt aqueous solution may be added simultaneously, or only the halogen salt aqueous solution may be added. After the halogen salt aqueous solution is added, the silver salt aqueous solution and the halogen salt aqueous solution are added. May be added simultaneously. Further, the silver salt aqueous solution and the halogen salt aqueous solution are mixed with a mixing device separate from the reaction solution to form silver halide fine particles, and then the fine particles are added to the reaction vessel to continue the epitaxial formation. Epitaxial formation may be continued by adding the prepared silver halide fine particles to the reaction vessel.

The epitaxial formation step may be performed continuously after tabular grain formation, may be performed after washing / redispersion once after tabular grain formation, or may be performed before chemical sensitization.
The epitaxial formation divided into several times may be performed continuously in the silver halide forming step, may be performed after washing / redispersion with water, or may be performed before chemical sensitization. Moreover, you may divide before and after washing / redispersion.

  Although dislocation lines may not exist in the epitaxial portion, it is more preferable that dislocation lines exist. The dislocation lines are preferably present at the junction between the host particle and the epitaxial growth portion or at the epitaxial portion. The average number of dislocation lines present is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

It is further preferable to introduce a “dopant (metal complex)” as described in JP-A-8-69069 into the epitaxial layer. Specifically, it is preferable that a 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 preferred. The addition amount of the metal complex is preferably in the range of 10 ^{−9 to} 10 ⁻² mol per mol of silver halide, and more preferably in the range of 10 ^{−8 to} 10 ⁻⁴ mol per mol of silver halide. preferable. The metal complex can be added by dissolving in water or an organic solvent. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols, ethers, glycols, ketones, esters, and amides.

  As the protective colloid used in preparing the emulsion of the present invention, it is advantageous to use the gelatin described above, 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 and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances 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 can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide, etc. (methionine content 40 μmol / g or less), amino group-modified gelatin (eg, phthalated gelatin, trimellitized) Gelatin, succinylated gelatin, maleated gelatin, esterified gelatin) are used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are described in Japanese Patent Publication No. 7-111550, Research Disclosure Magazine Vol. 176, No. 17643 (December 1978), section IX. The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but is preferably selected between 2 and 10. More preferably, it is the range of 3-8. The pAg at the time of washing can also be selected according to the purpose, but it is preferably selected from 5 to 10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, an ion exchange method, and an ultrafiltration method. In the case of the coagulation sedimentation method, 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 can be selected.

  At the time of grain formation of the present invention, it was described in, for example, JP-A-5-173268, JP-A-5-173269, JP-A-5-173270, JP-A-5-173271, JP-A-6-202258, and JP-A-7-175147. Polyalkylene oxide block copolymers or polyalkylene oxide copolymers described, for example, in US Pat. No. 3,089,578 may be present. The time when the compound is present may be any time during the preparation of the particles, but the effect is great when used at an early stage of particle formation.

In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, it is preferable that a metal ion salt is present before coating, depending on the purpose. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. A method of doping the entire particle and a method of doping only the core or only the shell of the particle can be selected. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₄ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) _{6], K 2 IrCl 6,} (NH 4) 3 RhCl 6, K 4 Ru (CN) 6 and the like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one kind of metal compound, but may be used in combination of two or more kinds.

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

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

  The silver halide grains of the present invention have a chalcogen sensitization such as sulfur sensitization, selenium sensitization or tellurium sensitization; noble metal sensitization such as gold sensitization or palladium sensitization; It can be applied in any step of the manufacturing process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion of the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.

  One chemical sensitization that 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 Theory of Photographic Process, 4th edition, published by McMillan, 1977, (TH James, The Theory of the Photographic Process, 4th ed, McCillan, 1977), page 67-76. Research Disclosure, 120, April, 1974, 12008; Research Disclosure, 34, June, 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, No. 3,772,031, No. 3,857,71 PAg 5-10, as described in US Pat. Nos. 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,315,755, It can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers at a pH of 5-8 and a temperature of 30-80 ° C. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable.

  In gold sensitization, P.I. Gold salts described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.

  Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, US Pat. No. 2,642,361 (such as gold sulfide and gold selenide), 3503749 (such as gold thiolate having a water-soluble group), No. 5049484 (bis (methylhydantoinato) gold complex, etc.), No. 5049485 (mesoionic thiolate gold complex, such as 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold complex) ), Macrocyclic heterocyclic complexes of 5252455 and 5391727, 5620841, 5700571, 5759760, 5759761, 5912111, 5912112, 5939245, JP-A-1-147537 No., 8-69074, No. 8-69075, No. -269554, Japanese Patent Publication No. 45-29274, East German Patent DD-264524A, 264525A, 265474A, 298321A, JP-A-2001-75214, 2001-75215, 2001-75216, 2001-75217 Gold compounds described in JP-A-2001-75218 can also be used.

The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.
Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.

  In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.

  Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, dicarboxymethyl- Dimethylthiourea, carboxymethyl-trimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethylrhodanine), phosphine sulfides (eg, trimethylphosphine) Sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates, Elemental Such known sulfur compounds and active gelatin, such as yellow may also be used. Particularly preferred are thiosulfates, thioureas, phosphine sulfides and rhodanines.

  In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, 4-109340, 4-271341, and 5-40324. 5-11385, 6-51415, 6-175258, 6-180478, 6-208184, 6-208186, 6-317867, 7-92599, Selenium compounds described in 7-98483, 7-140579 and the like can be used.

  Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (for example, selenoamide, N, N -Diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters (for example, methoxyphenylselenocarboxy-2,2-dimethoxycyclohexa) Ester), or the like may be used diacylselenides. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides, and the like may be used. it can. In particular, phosphine selenides, selenoureas, selenoesters and selenocyanic acids are preferred.

  In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595, JP-A-4-271341, JP-A-4-3333043, JP-A-5-303157, JP-A-6-27573, JP-A-6-175258, The unstable tellurium compounds described in JP-A-6-180476, JP-A-6-208184, JP-A-6-208186, JP-A-6-317867 and JP-A-7-140579 can be used.

  Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxydiphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis ( Ethoxycarbonyl) telluride), telluroureas (for example, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea) telluramides, telluroesters, etc. may be used.

  Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. It is described in the book “photographic emulsion chemistry”, pp. 138-143.

The amount of gold sensitizer and chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but is 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide, The amount is preferably about 10 ⁻⁷ to 10 ⁻³ mol.

The silver halide emulsion used in any of the silver halide emulsion layers of the silver halide color photographic light-sensitive material of the present invention is used during grain formation, after grain formation and before chemical sensitization or during chemical sensitization, or chemical sensitization. After the sensitization, reduction sensitization is performed in the presence of at least one sulfodihydroxyaryl compound represented by the following general formula (I) or (II). Reduction sensitization using this compound has the feature that fog is kept low when used in combination with a compound of type 1 or 2.

  In general formula (I) and (II), X and Y represent a sulfo group or a hydrogen atom. However, at least one of X and Y 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 an ammonium salt. Specific examples of preferable compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-6,7-di And sulfonaphthalene potassium salt.

  The preferred addition amount of the reduction sensitizer of the present invention depends on the emulsion production conditions such as the temperature of the system to be added, pBr, pH, type of protective colloid agent such as gelatin, concentration, presence or absence of silver halide solvent, type and concentration. Therefore, it is necessary to select the addition amount, but 0.0005 mol to 0.5 mol, more preferably 0.003 mol to 0.02 mol is used per mol of silver halide. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth.

  Other reduction sensitization methods, that is, a method of adding another reduction sensitizer to the silver halide emulsion, a method of growing or ripening in a low pAg atmosphere called silver ripening, pH 8 to called high pH ripening Any of the methods of growing or aging in an atmosphere of 11 high pH can be used in combination. The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.

  Other reduction sensitizers include, for example, stannous salts, ascorbic acid and its derivatives, hydroquinone and its derivatives, catechol and its derivatives, hydroxylamine and its derivatives, amines and polyamines, hydrazine and its derivatives, paraphenylene Examples include diamines and derivatives thereof, formamidine sulfinic acid (thiourea dioxide), silane compounds, and borane compounds. These reduction sensitizers can be selected and used in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, 3,930, Regarding the method disclosed in No. 867 and the method of using a reducing agent, the methods disclosed in JP-B-57-33572, JP-A-58-1410 and JP-A-57-179835 can be used. Catechol and its derivatives, hydroxylamine and its derivatives, and formamidine sulfinic acid (thiourea dioxide) are preferred compounds as reduction sensitizers.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H _{2). O 2, 2Na 2 SO 4 ·} H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compound ( For _{example, K 2 [Ti (O 2} ) C 2 O 4] · 3H 2 O, 4K 2 SO 4 · Ti (O 2) OH · SO 4 · 2H 2 O, Na 3 [VO (O 2) (C 2 H ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), oxyacid salts such as chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine Perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferric acid) and thio There is a sulfonate.

  Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).

  Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizers of thiosulfonates, and organic oxidizers of quinones. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. The method can be selected from a method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both. These methods can be selected and used in either the particle formation step or the chemical sensitization step.

  The photographic emulsion of the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control grain habit, reduce grain size, decrease grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

  The photographic emulsion of the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit 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 cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

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

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.

Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is carried out after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. Spectral sensitization can be performed simultaneously with chemical sensitization, or prior to chemical sensitization as described in JP-A-58-113928, and silver halide grains can be precipitated. Spectral sensitization can also be started by adding before completion of production. Further, as taught in U.S. Pat. No. 4,225,666, these compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder is chemically enhanced. It can be added after the sensitization, and may be any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

  In the present invention, it is also preferable to use a technique for improving the light absorption rate with a spectral sensitizing dye. For example, by utilizing intermolecular force, the sensitizing dye is adsorbed to the surface of the silver halide grain more than the saturated coating amount, or two or more separately unconjugated dye chromophores are covalently linked. A dye, a so-called linked dye, is adsorbed on silver halide grains, and is described in, for example, the following patents.

  JP 10-239789, JP 11-133531, JP 2000-267216, JP 2000-275772, JP 2001-75222, JP 2001-75247, JP 2001-75221, Special JP 2001-75226, JP 2001-75223, JP 2001-255615, JP 2002-23294, JP 2002-148767, JP 10-171058, JP 10-186559, JP 10-197980, JP 2000-81678, JP 2001-5132, JP 2001-166413, JP 2002-49113, JP 64-91134, JP 10-110107, JP 10-171058, JP 10-226758, JP 10-307358, JP 10-307359, JP 10-310715, JP 2000-231174, JP 2000-231172, JP 2000 -231173, JP-A-2001-356442, European Patent No. 985965A, European Patent No. 985964A, European Patent No. 985966A, European Patent No. 985967A, European Patent No. 1085372A, European Patent No. 1085373A, European Patent No. No. 1172688A, European Patent No. 1199595A, European Patent No. 887700A1.

  The emulsion of the present invention can be used for any photosensitive material, but is preferably used for a multilayer color photographic photosensitive material. It is more preferably used for the blue-sensitive layer of the multilayer color photographic light-sensitive material, and most preferably used for the highest blue-sensitive layer of the multilayer color photographic light-sensitive material. At this time, especially when the silver iodide content is high, a high sensitivity / granularity ratio due to an increase in blue light absorption and an increase in blue light absorption based on an increase in sensitizing dye adsorption due to the plate shape. Is obtained. In addition, by improving the monodispersity of the projected area diameter of the grains and decreasing the silver iodide content distribution between grains, the high sensitivity / grain ratio, improved pressure characteristics, improved storage aging characteristics and processing dependency Improvements can be achieved. Further, the scattering of light is reduced by the flat plate shape, and the sharpness of the lower layer is improved.

  The light-sensitive material of the present invention is a color photographic light-sensitive material in which at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer is provided on a support. There are no particular restrictions on the number and order of the silver halide emulsion layer and the non-light-sensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Are arranged in the order of the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are contained in the same color-sensitive layer.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide light-sensitive layers and on the uppermost layer and the lowermost layer.
The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-113438, 59-113440, 61-20037, and 61-20038. And may contain an anti-color mixing agent as commonly used.

  A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure can be preferably used. In general, it is preferable that the photosensitivity is gradually decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, the low-sensitivity emulsion layer is close to the support on the side away from the support. A high-sensitivity emulsion layer may be provided on the side.

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

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

  In addition, 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 more sensitive than the middle layer. A silver halide emulsion layer having a low photosensitivity is arranged, and an arrangement composed of three layers having different photosensitivities in which the photosensitivity is gradually lowered toward the support. Even in the case of the three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitive emulsion layer / from the side away from the support in the same color-sensitive layer / They may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer.

In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
Further, the arrangement may be changed as described above even when there are four or more layers.

Further, a layer containing silver halide tabular grains that do not form an image after exposure processing may be disposed. The emulsion layer may not be adjacent to the emulsion layer according to the first aspect of the present invention, but is preferably adjacent to the emulsion layer according to the first aspect of the present invention so as to be close to the support. It is preferred that Specifically, the silver halide tabular grains that do not form an image preferably have a grain thickness of 0.02 μm or more and 0.2 μm or less, and more preferably 0.05 μm or more and 0.15 μm or less. The particle size is preferably 0.05 μm or more and 2.0 μm or less, and more preferably 0.1 μm or more and 1.5 μm or less. The average silver iodide content of the silver halide grains is preferably 3 mol% or less, more preferably 2 mol% or less, based on the total Ag amount. The silver halide emulsion that does not form an image is preferably basically not subjected to chemical image processing, but a silver halide adsorbing material may be adsorbed to stabilize the dye or silver halide grains. The silver halide grains that do not form an image in the silver halide emulsion layer that does not form an image preferably contain 0.1 g / m ² or more and 2.0 g / m ² or less in terms of Ag, and more than 0.2 g / m ² 1.0 g / m ² or less is more preferable. The silver halide tabular grains that do not form an image may have a tabular grain thickness that reflects light of a specific wavelength as described in JP-A Nos. 2000-305228 and 2000-314940. good. Specifically, tabular grains having such a thickness that the emulsion layer according to claim 1 of the present invention, in which the emulsion layer where no image is formed, is adjacent to the indicator, has strong reflection in the wavelength range to which light is exposed may be used. However, the thickness need not be set so as to reflect a specific wavelength.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but various additives can be used depending on the purpose.
These additives are more specifically described in Research Disclosure Item
17643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989), the corresponding portions are shown in the table below.

Additive type RD17643 RD18716 RD308119
1 Chemical sensitizer page 23 page 648 right column page 996
2 Sensitivity increasing agent Same as above
3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right supersensitizer, page 649, right column
4 Brightener 24 pages 647 right column 998 right
5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right and stabilizer
6 Light absorber, page 25-26, page 649, right column to 1003, left to 1003 right Filter dye, page 650, left column, UV absorber
7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right
8 Dye image stabilizer 25 page 1002 right
9 Hardener page 26 page 651 left column 1004 right to 1005 left
10 Binder page 26 Same as above 1003 right to 1004 right
11 Plasticizer, Lubricant 27 pages 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 Anti-blocking agent
14 Matting agent 1008 left to 1009 left

  Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503 is immobilized on a photosensitive material. It is preferable to add.

  Various color couplers can be used in the present invention, and specific examples thereof are the above-mentioned Research Disclosure No. 17643, VII-CG and No. 307105, described in the patents described in VII-CG.

  Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat. No. 3,973,968, No. 4,314,023, No. 4 511,649, European Patent No. 249,473A, and the like.

  The magenta coupler is preferably a 5-pyrazolone compound or a pyrazoloazole compound. US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, US Pat. No. 061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730, 55-1118034, 60-185951, US Pat. No. 4,500,630, Nos. 4,540,654, 4,556,630, and International Publication WO88 / 04795 are particularly preferable.

  Examples of cyan couplers include phenolic and naphtholic couplers, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3 758,308, 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4, No. 690,889, No. 4,254,212 The No. 4,296,199, are preferred according to JP-61-42658 or the like.

  Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, No. 4,576,910, British Patent No. 2,102,137 and European Patent No. 341,188A.

  As couplers in which the coloring dye has an appropriate diffusibility, U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) 3,234 No. 533 is preferred.

  Colored couplers for correcting unwanted absorption of chromogenic dyes are Research Disclosure No. No. 17643, VII-G, No. No. 307105, VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, British Patent 1,146, Those described in No. 368 are preferred. Further, it reacts with a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling described in US Pat. No. 4,774,181, and a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

  Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release a development inhibitor include the above-mentioned RD17643, item VII-F, and No. 1 above. 307105, patents described in paragraph VII-F, JP-A-57-151944, 57-154234, 60-184248, 63-37346, 63-37350, US Pat. No. 4,248 No. 962, and No. 4,782,012 are preferred.

  Examples of couplers that release a nucleating agent or development accelerator in the form of an image during development include British Patent Nos. 2,097,140, 2,131,188, JP-A-59-157638, and 59-170840. Are preferred. Further, a fogging agent and a development accelerator are obtained by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687. Also preferred are compounds that release silver halide solvents and the like.

  Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472 and 4,338,393. No. 4,310,618, etc. Multi-equivalent couplers, JP-A-60-185950, JP-A-62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing A redox compound or a DIR redox releasing redox compound, a coupler that releases a dye that recovers color after release described in European Patent Nos. 173,302A and 313,308A; No. 11449, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,555,477, and leucos described in JP-A-63-75747. Examples include couplers that release a dye, and couplers that release a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
Examples of high boiling solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.

  Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). Bis (2,4-di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid Esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate Benzoates (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg N, N-diethyldodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis ( 2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylanily) ); Hydrocarbons (e.g., can be exemplified paraffin, dodecylbenzene, and diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone. , Cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

  Examples of latex dispersion process steps, effects and impregnating latexes are described in, for example, US Pat. No. 4,199,363, West German Patent Application (OLS) No. 2,541,274, and No. 2,541,230. In the issue.

  Examples of the color light-sensitive material of the present invention include phenethyl alcohol and those described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941, for example, 1,2-benzisothiazolin-3-one. Various preservatives or fungicides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole It is preferable.

  The emulsion of the present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper can be given as representative examples. The present invention can be particularly preferably used for a film for color duplication.

  Suitable supports that can be used for the light-sensitive material containing the emulsion of the present invention include, for example, the aforementioned RD. No. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and 307105, page 879.

In the light-sensitive material containing the emulsion of the present invention, the total thickness of all hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and 16 μm or less. Is particularly preferred. The membrane swelling speed T1 _{/ 2} is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness here means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days). The film swelling rate T _1/2 can be measured according to a method known in the art, and for example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng. ), Vol. 19, No. 2, pp. 124-129. Note that T _1/2 is 90% of the maximum swollen film thickness that is reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer, and is the time required to reach 1/2 of the saturated film thickness. Define.

The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

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

  The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, ibid. No. 18716, page 651, left column to right column; 307105, pages 880-881, and can be developed by a conventional method.

  The color developer used for the development processing of the light-sensitive material containing the emulsion of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -Β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates of these. Of these, sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferable. These compounds may be used in combination of two or more depending on the purpose.

  Color developers include, for example, pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include a development inhibitor or an antifogging agent. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting Agents: Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid can be used. Examples of chelating agents include ethylenediaminetetraacetic acid, nitrile triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N- Typical examples include trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

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

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The opening ratio is preferably 0.1 or less, more preferably 0. 001 to 0.05. As a method for reducing the aperture ratio in this way, a movable lid described in JP-A-1-82033 is used in addition to a method of providing a shielding object such as a floating lid on the photographic processing liquid surface of the processing tank. And a slit developing method described in JP-A-63-216005. The reduction of the aperture ratio is preferably applied not only in both color development and black-and-white development but also in subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Further, the replenishment amount can be reduced by using a means for suppressing the accumulation of bromide ions in the developer.

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

  The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after the bleaching processing may be used. Further, depending on the purpose, it is possible to carry out the treatment in two continuous bleach-fixing baths, the fixing treatment before the bleach-fixing treatment, or the bleaching treatment after the bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III), peracids (especially sodium persulfate is suitable for a color negative film for movies), quinones and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Complex salts with aminopolycarboxylic acids or complex salts with, for example, citric acid, tartaric acid and malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salts of ethylenediaminetetraacetic acid and 1,3-diaminopropanetetraacetic acid are the viewpoints of rapid processing and prevention of environmental pollution. To preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8, but the processing can be performed at a lower pH in order to speed up the processing.

  A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, and 2,059,988. JP-A-53-32736, 53-57831, 53-37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424. 53-141623, 53-18426, Research Disclosure No. Compounds having mercapto groups or disulfide groups described in JP-A No. 17129 (July 1978); thiazolidine derivatives described in JP-A No. 51-14129; JP-B Nos. 45-8506, 52-20832 and 53 No. -32735, a thiourea derivative described in US Pat. No. 3,706,561, an iodide salt described in West German Patent No. 1,127,715 and JP-A No. 58-16235; West German Patent No. 966,410 No. 2,748,430; polyoxyethylene compounds described in JP-B No. 45-8836; other JP-A Nos. 49-40943, 49-59644, 53-94927 No., 54-35727, 55-26506, 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly described in US Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630. Are preferred. Furthermore, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed.

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

  Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, a combination of thiosulfate and, for example, thiocyanate, thioether compound, or thiourea is also preferable. As the preservative for the fixing solution or the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

  In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc. It is preferable to add imidazoles in an amount of 0.1 to 10 mol / liter.

  The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved, and the occurrence of stain after the treatment is effectively prevented.

  In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring include the method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means in JP-A-62-183461. The method of raising the effect is mentioned. Furthermore, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the emulsion surface is turbulent to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. The method of letting it be mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is considered to speed up the supply of the bleaching agent and the fixing agent into the emulsion film and consequently increase the desilvering rate. Further, the above stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibiting action can be eliminated by the bleaching accelerator.

  An automatic developing machine used for developing a photosensitive material containing the emulsion of the present invention has photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. It is preferable. As described in JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance deterioration of the processing liquid. Such an effect is particularly effective in shortening the processing time in each process and reducing the replenishment amount of the processing liquid.

  The silver halide color photographic light-sensitive material containing the emulsion of the present invention is generally subjected to a washing and / or stabilizing process after desilvering. The amount of water to be washed in the washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, and further, for example, the temperature of the washing water, the number of washing tanks (number of stages), replenishment such as countercurrent and forward flow A wide range can be set according to the system and other various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent system is described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, p. 248 to 253 (May 1955).

  According to the multi-stage countercurrent system described in the above-mentioned document, the amount of water to be washed can be greatly reduced. However, bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Further, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others such as benzotriazole, written by Horiguchi Hiroshi “Chemistry of Antibacterial and Antifungal Agents” (1986) Sankyo Publishing, Hygiene Technology Association “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association of Japan The fungicides described in “Enamel Encyclopedia” (1986) can also be used.

  The pH of the washing water in the processing of the light-sensitive material containing the emulsion of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and application of the photosensitive material. In general, the washing water temperature and washing time are 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. A range is selected. Furthermore, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, all known methods described in JP-A-57-8543, 58-14834, and 60-220345 can be used.

  Further, a stabilization treatment may be further performed following the water washing treatment. Examples thereof include a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow liquid accompanying the washing with water and / or the replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process.
For example, in the processing using an automatic developing machine, when each processing solution is concentrated by evaporation, it is preferable to correct the concentration by adding water.

  The silver halide color photographic light-sensitive material containing the emulsion of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of color developing agents. For example, an indoaniline compound described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. No. 15,159, Schiff base type compounds, An aldol compound described in US Pat. No. 13,924, a metal salt complex described in US Pat. No. 3,719,492, and a urethane compound described in JP-A-53-135628 can be used.

  The silver halide color photographic material containing the emulsion of the present invention may incorporate various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described, for example, in JP-A Nos. 56-64339, 57-144547, and 58-115438.

  The various processing liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but the temperature is increased to accelerate the processing and shorten the processing time, or conversely, the temperature is lowered to achieve an improvement in image quality and stability of the processing solution. be able to.

The silver halide light-sensitive material containing the emulsion of the present invention is disclosed in U.S. Pat. No. 4,500,626, JP-A-60-133449, 59-218443, 61-238056, and European Patent 210. , 660A2 and the like.
The silver halide color photographic light-sensitive material containing the emulsion of the present invention is more effective when applied to a lens-attached film unit described in JP-B-2-32615, JP-B-3-39784, etc. It is easy to express and is effective.

Examples of the present invention are shown below. However, the present invention is not limited to this example.
(Example 1)
(Preparation of multilayer coating sample and its evaluation)
1) Support The support used in this example was prepared by the following method.
100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-shaped die, and stretched 3.3 times at 140 ° C., followed by 130 ° C. The film was stretched by 3.3 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public techniques: I-1, I-4, I-6, I-24, I-26, I-27 described in public technical number 94-6023). II-5) was added in an appropriate amount. Further, it was wound around a stainless steel core having a diameter of 20 cm to give a thermal history of 110 ° C. and 48 hours, thereby providing a support that is difficult to curl.

2) Coating of subbing layer The support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m ² and sodium α-sulfo di- 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 / An undercoat solution of m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² was applied (10 cc / m ² , using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as a back layer on one side of the support after the undercoating.
3-1) Coating of antistatic layer The specific resistance of the tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm is 0 of a dispersion of fine powder of 5 Ω · cm (secondary aggregate particle diameter of about 0.08 μm). .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02g / m 2, poly (polymerization degree 10) oxyethylene -p- nonylphenol 0. 005 g / m ² and resorcin.

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, (Major axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89Am ² / kg, Fe ⁺² / Fe ⁺³ = 6/94, the surface is treated with 2% by mass of iron oxide with silicon oxide oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H 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. 10 mg each of abrasive aluminum oxide (0.15 μm) treated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as a matting agent / M ² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transporting devices in the drying zone were 115 ° C.). X- light (blue filter) saturation magnetization moment of about 0.1, and the magnetic recording layer is color density increment of D ^B of the magnetic recording layer of the 4.2Am ² / kg, a coercive force 7.3 × 10 ⁴ A / m, the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1) and pouring and dispersing in propylene monomethyl ether at room temperature (10 times the amount). The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum particles (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as a matting agent It added so that it might become ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard balls, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clipping method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later is 0.12. Excellent characteristics.

4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in layers to prepare a sample 101 as a color negative photosensitive material.
Table 1 shows the characteristics of the silver halide emulsion Em-A1 to O.

For the 14th layer emulsion A1 (described in Example 1 of JP-A-2004-37936, with K ₄ [Ru (CN) ₆ ] removed), the reduction sensitizer 3,5-disulfocateco of the present invention is used. -The compound was changed to rudisodium salt, the compound 7 of the present invention was added 3 × 10 ^-6 mol / mol Ag (Ag of emulsion A1), or the emulsion A2 of the present invention (in JP-A-2004-37936, Example 1) Description, except that K ₄ [Ru (CN) ₆ ] is removed), the heterocyclic compound (a-22) of the present invention is added, or B ₁₀ -3 of the present invention is added to 1 × 10 ⁻² Samples 102 to 110 as shown in Table 2 were prepared by adding mol / mol Ag (Ag of emulsion A1). In addition, in the emulsion A1, the grains satisfying the epitaxial requirements (requirement (c)) defined in this specification account for 23% of the total projected area. In emulsion A2, the grains satisfying the requirement (c) occupy 63% of the total projected area.

(Composition of photosensitive layer)
The main materials used in 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 hardener The number corresponding to each component (in which the chemical formula is given) indicates the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver.

First layer (first antihalation layer)
Black colloidal silver Silver 0.043
Gelatin 0.66
ExM-1 0.048
Cpd-2 0.001
F-8 0.001
HBS-1 0.090
HBS-2 0.010

Second layer (second antihalation layer)
Black colloidal silver Silver 0.043
Gelatin 0.80
ExM-1 0.057
ExF-1 0.002
F-8 0.001
HBS-1 0.090
HBS-2 0.010

Third layer (intermediate layer)
ExC-2 0.010
Cpd-1 0.086
UV-2 0.029
UV-3 0.052
UV-4 0.011
HBS-1 0.100
Gelatin 0.600

4th layer (low sensitivity red sensitive emulsion layer)
Em-M Silver 0.175
Em-N Silver 0.211
Em-O Silver 0.043
ExC-1 0.222
ExC-2 0.010
ExC-3 0.072
ExC-4 0.148
ExC-5 0.005
ExC-6 0.008
ExC-8 0.071
ExC-9 0.010
UV-2 0.036
UV-3 0.067
UV-4 0.014
Cpd-2 0.010
Cpd-4 0.012
HBS-1 0.240
HBS-5 0.010
Gelatin 1.500

5th layer (medium sensitivity red emulsion layer)
Em-L Silver 0.160
Em-M Silver 0.110
ExC-1 0.111
ExC-2 0.039
ExC-3 0.018
ExC-4 0.074
ExC-5 0.019
ExC-6 0.024
ExC-8 0.010
ExC-9 0.021
Cpd-2 0.020
Cpd-4 0.021
HBS-1 0.129
Gelatin 0.850

6th layer (high-sensitivity red-sensitive emulsion layer)
Em-K Silver 1.490
ExC-1 0.122
ExC-6 0.032
ExC-8 0.110
ExC-9 0.005
ExC-10 0.159
Cpd-2 0.068
Cpd-4 0.015
HBS-1 0.440
Gelatin 1.510

7th layer (intermediate layer)
Cpd-1 0.081
Cpd-6 0.002
Solid disperse dye ExF-4 0.015
HBS-1 0.049
Polyethyl acrylate latex 0.088
Gelatin 0.800

Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Em-E silver 0.170
Cpd-4 0.010
ExM-2 0.082
ExM-3 0.006
ExM-4 0.026
ExY-1 0.010
ExY-4 0.040
ExC-7 0.007
HBS-1 0.203
HBS-3 0.003
HBS-5 0.010
Gelatin 0.520

9th layer (low sensitivity green emulsion layer)
Em-H Silver 0.064
Em-I Silver 0.098
Em-J Silver 0.100
ExM-2 0.388
ExM-3 0.040
ExY-1 0.003
ExY-3 0.002
ExC-7 0.009
HBS-1 0.337
HBS-3 0.018
HBS-4 0.260
HBS-5 0.110
Cpd-5 0.010
Gelatin 1.450

10th layer (medium sensitive green sensitive emulsion layer)
Em-G Silver 0.117
Em-H Silver 0.051
ExM-2 0.084
ExM-3 0.012
ExM-4 0.005
ExY-3 0.002
ExC-6 0.003
ExC-7 0.007
ExC-8 0.008
HBS-1 0.096
HBS-3 0.002
HSB-5 0.002
Cpd-5 0.004
Gelatin 0.420

11th layer (high sensitivity green emulsion layer)
Em-F Silver 1.42
ExC-6 0.002
ExC-8 0.010
ExM-1 0.014
ExM-2 0.023
ExM-3 0.023
ExM-4 0.005
ExM-5 0.040
ExY-3 0.003
Cpd-3 0.004
Cpd-4 0.007
Cpd-5 0.010
HBS-1 0.259
HBS-5 0.020
Polyethyl acrylate latex 0.099
Gelatin 1.110

12th layer (yellow filter layer)
Cpd-1 0.088
Oil-soluble dye ExF-2 0.051
Solid disperse dye ExF-8 0.010
HBS-1 0.049
Gelatin 0.540

13th layer (low sensitivity blue-sensitive emulsion layer)
Em-B Silver 0.203
Em-C Silver 0.064
Em-D Silver 0.043
ExC-1 0.024
ExC-7 0.011
ExY-1 0.002
ExY-2 0.956
ExY-4 0.091
Cpd-2 0.037
Cpd-3 0.004
HBS-1 0.372
HBS-5 0.047
Gelatin 2.000

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-A1 (described in Example 1 of JP-A-2004-37936) Silver 1.44
ExY-2 0.235
ExY-4 0.018
Cpd-2 0.075
Cpd-3 0.001
HBS-1 0.087
Gelatin 1.300

15th layer (first protective layer)
Silver iodobromide emulsion Silver 0.105
(Average particle size: equivalent sphere equivalent diameter 0.07 μm)
UV-1 0.358
UV-2 0.179
UV-3 0.254
UV-4 0.025
F-11 0.008
S-1 0.078
ExF-5 0.0024
ExF-6 0.0012
ExF-7 0.0010
HBS-1 0.175
HBS-4 0.050
Gelatin 1.800

16th layer (second protective layer)
H-1 0.400
B-1 (diameter 1.7 μm) 0.050
B-2 (diameter 1.7 μm) 0.150
B-3 0.050
S-1 0.200
Gelatin 0.750

  Furthermore, in order to improve storage stability, processability, pressure resistance, antibacterial / antibacterial properties, antistatic properties and coatability as appropriate for each layer, W-1 to W-5, B-4 to B-6, F-1 thru | or F-17 and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, ruthenium salt, rhodium salt are contained.

The effect of the emulsion produced by the production method of the present invention in a multilayer color photographic light-sensitive material is shown.
These emulsions were prepared by appropriate selection, combination and / or modification based on the contents of the following patent texts and / or examples.
Regarding the structure, chemical sensitization, spectral sensitization, etc. of the emulsion, in particular, European Patent No. 573649B1, Patent No. 2912768, JP-A-11-249249, JP-A-11-295832, JP-A-11-72860, US Patent No. No. 5985534, U.S. Pat.No. 5953443, No. 3002715, No. 3045624, No. 3045623, JP 2000-275771, U.S. Pat.No. 6172110, JP 2000-321702, JP 2000-321700 , JP 2000-321698, U.S. Pat.No. 6,153,370, JP 2001-92065, JP 2001-92064, JP 2000-92059, JP 2001-147501, US Patent Application 2001 / 0006768A1 , JP 2001-228572, JP 2001-255613, JP 2001-264911, U.S. Pat.No. 6,280,920B1, JP 2001-264912, JP 2001-281778, U.S. Patent Application Publication 2001 / 003143A1 Based on the description.

  Regarding the production method of the emulsion, Japanese Patent No. 2878903, Japanese Patent Laid-Open No. 11-143002, Japanese Patent Laid-Open No. 11-143003, Japanese Patent Laid-Open No. 11-174612, US Pat. No. 5,925,508, US Pat. U.S. Patent No. 5989800, Patent No. 3005382, Patent No. 3014235, European Patent No. 04315858B1, U.S. Patent No. 6040127, Patent No. 3049647, Patent No. 3045622, Patent No. 30669682, European Patent No. 0563708B1, Patent No. 3091041, JP 2000-338620, JP 2001-83651, JP 2001-75213, JP 2001-100343, US Patent 651577B1, European Patent 0563701B1, JP 2001-281780 No., US Patent Application Publication No. 2001 / 0036606A1, and the like.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-4 below was dispersed by the following method. That is, 21.7 mL of water and 3 mL of 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 5.0 g of dye ExF-3 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and 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 diameter of the dye fine particles was 0.44 μm.
The oil-soluble dye ExF-2 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.

A solid dispersion of ExF-8 was dispersed by the following method.
To 2800 g of ExF-8 wet cake containing 18% of water, 376 g of 4000 g of water and a 3% solution of W-2 was added and stirred to obtain a slurry of ExF-8 having a concentration of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm were filled in Ultra Visco Mill (UVM-2) manufactured by IMEX Co., Ltd., and pulverized for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min through the slurry. did. The average particle size was 0.45 μm.
The compounds used for forming each of the above layers are as shown below.

  These samples 101 to 110 were subjected to hardening for 14 hours under the conditions of 40 ° C. and 70% relative humidity. Thereafter, the sample was subjected to 1/100 second exposure through a gelatin filter SC-39 (long wavelength light transmission filter with a cut-off wavelength of 390 nm) manufactured by Fuji Film Co., Ltd. and a continuous wedge. The photographic sensitivity and the fog were evaluated by measuring the density with a green filter and a blue filter.

  Development was performed as follows using Fuji Photo Film Co., Ltd. automatic organ FP-360B. In addition, a modification was made so that the overflow solution of the bleaching bath was not discharged to the rear bath but was discharged to the waste solution tank. This FP-360B is equipped with the evaporation correction means described in the Invention Association Open Technique 94-4992.

The treatment process and the treatment liquid composition are shown below.
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ -5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Washing with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ -3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)

The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching step, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL for a photosensitive material 35 mm width 1.1 m, respectively. 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic 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-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
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

(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium 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 aqueous ammonia] 4.6 4.0

(Fixing (1) Tank liquid)
5 to 95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution (pH 6.8)

(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 is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-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
Add water and add 1.0L
pH 8.5

The results of photographic sensitivity, fogging and raw storage stability are shown in Table 3 below. Sensitivity is displayed as a relative value of the reciprocal of the exposure amount necessary to reach the fog density plus 0.15 density of the obtained yellow, magenta and cyan density characteristic curves (the sensitivity of the sample 101 is 100). ). The raw storability is that when each sample is stored in a Thermocellco at 60 ° C. and 60% for 4 days and when stored at 25 ° C. and 55% for 4 days, each sample is subjected to the above-mentioned exposure, development and density measurement, and 60 ° C. at 60 ° C. The difference in fog and the blue sensitivity when stored in a thermocellco for 4 days and at 25 ° C. for 4 days are expressed as Δfog and ΔS, respectively.

From the above results, by using the compound 7 of the present invention capable of releasing one electron or two electrons, the reduction sensitizer 3,5 disulfocatechol disodium of the present invention, and the compound B ₁₀ -3 of the present invention in combination. It can be seen that a silver halide color photographic light-sensitive material having high sensitivity, low fog and excellent storage stability can be obtained. Furthermore, it can be seen that a silver halide color photographic light-sensitive material having higher sensitivity and lower fog and excellent storage stability can be obtained by combining the epitaxial emulsion of the present invention and the heterocyclic compound of the present invention.

(Example 2)
In Sample 505 of Example 5 of JP-A-2001-142170, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). By performing the same evaluation as in Example 1 and using the compound capable of releasing one electron or two electrons of the present invention in combination with the reduction sensitizer of the present invention, the pressure property is improved in tabular grains in a large size region. In the sensitive material, high sensitivity, low fog and excellent storage stability were obtained.

(Example 3)
In the sample 202 of Example 4 of JP-A No. 2001-159799, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was conducted, and the compound of the present invention capable of emitting one electron or two electrons or more was used in combination with the reduction sensitizer of the present invention. , High sensitivity, low fogging and excellent storage stability were obtained.

Example 4
In Sample 905 of Example 7 of JP-A-2000-347336, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was carried out, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, whereby the sensitization having inorganic fine particles in the dispersion medium phase of the emulsion. In the material, high sensitivity, low fog and excellent storage performance were obtained.

(Example 5)
In the sample 904 of Example 9 of JP-A No. 11-295832, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, so that iodide ions were rapidly released from the iodide ion releasing agent. In the emulsion having a high iodine layer formed by forming, a high sensitivity, low fog and excellent storage stability were obtained.

(Example 6)
In Sample 222 of Example 8 of JP-A No. 2000-321698, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the highly sensitive blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, whereby the aspect ratio was 8 or more and the average iodine content was 2 mol. As described above, in an emulsion having 10 or more dislocation lines and a coefficient of variation of intergranular iodine distribution of 20% or less, high sensitivity, low fog and excellent storage stability were obtained.

(Example 7)
In sample 109 of Example 1 of JP-A No. 2000-231175, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. was gotten.

(Example 8)
In the sample 302 of Example 3 of JP-A-2001-324773, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. was gotten.

Example 9
Infrared absorbing dyes (62), (63), (64), (72), (74), (87) of JP-A-9-96891 are introduced into the second layer of Example 1 of the present invention, and high sensitivity By using the compound capable of emitting one or more electrons of Example 1 of the present invention in combination with the reduction sensitizer of the present invention and the compound of the general formula (B ₁₀ ) of the present invention in the blue sensitive emulsion layer, a sample was prepared. Created. The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. was gotten.

(Example 10)
In the sample 403 of Example 4 of JP-A-2001-228572, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of emitting one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. A silver iodide or silver iodochlorobromide tabular grain having a variation coefficient of 40 to 3% and having a (111) plane as the main surface, having an equivalent circle equivalent diameter of 1.0 μm or more and a grain thickness of 0.10 μm or less. In the emulsion having no part of the sides and corners, high sensitivity, low fog and excellent storage stability were obtained.

(Example 11)
In the sample of Example 6 of JP-A No. 2001-264911, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the present invention in general. A sample was prepared by using in combination with a compound of formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. In the light-sensitive material improved in, high sensitivity, low fogging and excellent storage performance were obtained.

(Example 12)
In the sample 713 of Example 7 of JP-A-2001-281778, the compound capable of releasing one electron or two electrons of Example 1 of the present invention is used in combination with the reduction sensitizer of the present invention in the high-sensitivity blue-sensitive emulsion layer. Thus, a sample was prepared. By performing the same evaluation as in Example 1, and using the compound of the present invention capable of releasing one electron or two electrons in combination with the reduction sensitizer of the present invention and the compound of the general formula (B ₁₀ ) of the present invention, A silver iodobromide or silver iodochlorobromide grain with a thickness of 0.1 μm or less, and an emulsion having a silver iodobromide phase in which an annual ring structure is not observed inside the grain, with high sensitivity, low fog and storage stability Excellent performance was obtained.

(Example 13)
In the sample 205 of Example 2 of JP-A-2001-296627, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). Non-tabular grains produced in the preparation of tabular grains by performing the same evaluation as in Example 1 and using the compound capable of releasing one electron or two electrons of the present invention in combination with the reduction sensitizer of the present invention, In particular, in an emulsion in which the formation of rod-like grains was reduced, high sensitivity, low fog and excellent storage stability were obtained.

(Example 14)
In the sample 303 of Example 3 of JP-A No. 2002-169240, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). An emulsion in which the dissolution time stability of the coating solution is improved by performing the same evaluation as in Example 1 and using the compound capable of releasing one electron or two electrons of the present invention in combination with the reduction sensitizer of the present invention. , High sensitivity, low fogging and excellent storage stability were obtained.

(Example 15)
In Sample 205 of Example 2 of JP-A-2001-255613, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). By performing the same evaluation as in Example 1 and using the compound capable of emitting one or more electrons of the present invention in combination with the reduction sensitizer of the present invention, a (111) flat plate having a small pressure fog in a large size region. In the particles, high sensitivity, low fogging and excellent storage performance were obtained.

(Example 16)
In the sample 304 of Example 3 of JP-A No. 2002-268162, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). In the tabular grains having the same evaluation as in Example 1 and using the compound capable of releasing one electron or two electrons of the present invention in combination with the reduction sensitizer of the present invention, the fog at the time of storage is reduced, High sensitivity, low fog and excellent storage stability were obtained.

(Example 17)
In the sample 209 of Example 3 of JP-A No. 2001-235721, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, so that the silver chloride content was 1 to 6 mol%, iodine In a complete epitaxial emulsion having a silver halide content of 0.5 to 10 mol%, high sensitivity, low fog and excellent storage stability were obtained.

(Example 18)
In the sample 202 of Example 4 of JP-A-2002-169241, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. A silver tabular grain emulsion having an epitaxial junction at at least one apex portion has high sensitivity, low fog and excellent storage stability.

(Example 19)
In Example 3 of JP-A-2002-278008, the compound capable of releasing one electron or two electrons or more of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is represented by the reduction sensitizer of the present invention and the general formula ( by using in combination with the compounds of the B _10), were prepared samples. The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. In an emulsion having a silver halide tabular grain and an epitaxial junction having a silver chloride content of at least one vertex of a hexagonal shape of 5 to 25 mol%, a high sensitivity, low fog and excellent storage stability were obtained.

(Example 20)
In the sample 303 of Example 3 of JP-A-2002-169239, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. A silver halide tabular grain emulsion having an equivalent circle diameter of 3 μm or more and an aspect ratio of 8 or more and having an epitaxial junction has high sensitivity, low fog and excellent storage stability.

(Example 21)
In Sample 101 of Example 5 of JP-A-7-134351, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, thereby containing a hydrazine compound as an adsorbing group to silver halide. In the photosensitive material, high performance, low fog and excellent storage performance were obtained.

(Example 22)
In the sample 602 of Example 6 of JP-A-2000-250157, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). In the light-sensitive material containing the bispyridinium salt compound, the same evaluation as in Example 1 was performed, and the compound capable of emitting one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. Performance with excellent sensitivity and low fog was obtained.

(Example 23)
In sample 218 of Example 2 of JP-A-9-251193, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer was used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, so that the dispersion medium solution in the nucleation process was used in the emulsion production method. Emulsions containing low molecular weight gelatin with a molecular weight of 70,000 to 1000 and chemically modified gelatin having a chemical modification rate of 15 to 100% in the growth process have high sensitivity, low fog and excellent storage stability Performance was obtained.

(Example 24)
In the sample 103 of Example 2 of JP-A No. 2001-100343, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). The same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention, whereby the grain growth was 40 masses of the dispersion medium in the emulsion production method. In an emulsion prepared in the presence of more than 1% chemically modified gelatin or low molecular weight gelatin, high sensitivity, low fog and excellent storage stability were obtained.

(Example 25)
In the sample 305 of Example 3 of JP-A-2001-281780, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). Emulsion containing gelatin containing a large amount of high molecular weight component by performing the same evaluation as in Example 1 and using the compound capable of emitting one electron or two electrons of the present invention in combination with the reduction sensitizer of the present invention. , High sensitivity, low fogging and excellent storage stability were obtained.

(Example 26)
In the sample 203 of Example 3 of JP-A-3-39946, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). In the tabular emulsion containing mercaptobenzthiazole compounds, the same evaluation as in Example 1 was performed, and the compound capable of releasing one electron or two electrons of the present invention was used in combination with the reduction sensitizer of the present invention. High sensitivity, low fog, and excellent storage stability were obtained.

(Example 27)
In the sample 001 of Example 1 of JP-A-2001-75242, the compound capable of releasing one electron or two electrons of Example 1 of the present invention into the high-sensitivity blue-sensitive emulsion layer is used as the reduction sensitizer of the present invention and the compound of the present invention. A sample was prepared by using in combination with the compound of the general formula (B ₁₀ ). By performing the same evaluation as in Example 1 and using the compound capable of releasing one electron or two electrons of the present invention in combination with the reduction sensitizer of the present invention, high sensitivity and faithful reduction of green tint as much as possible. In the sensitive material that made it possible to reproduce colors, high sensitivity, low fog and excellent storage stability were obtained.

FIG. 1 is a schematic diagram of a cross section of an emulsion grain having an epitaxial structure which can be preferably used in the silver halide light-sensitive material of the present invention.

Claims (4)

In a silver halide color photographic material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer, respectively, on a support, the silver halide emulsion layer The silver halide emulsion contained therein is subjected to reduction sensitization in the presence of at least one sulfodihydroxyaryl compound represented by the following general formula (I) or (II). A silver halide color photographic light-sensitive material comprising a light-sensitive material containing at least one compound selected from the following types 1 and 2 and a compound represented by the general formula (B ₁₀ ):

In general formula (I) and (II), X and Y represent a sulfo group or a hydrogen atom. However, at least one of X and Y represents a sulfo group.
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

In the general formula _{(B 10), R b100,} R b101, R b102 each independently represent a hydrogen atom or a substituent. Z ₁₀ represents a nonmetallic atomic group that can form a ring with —C═CO—. More than 50% of the total projected area of the silver halide emulsion grains subjected to reduction sensitization is occupied by silver halide grains satisfying the following (a), (b), and (c): The silver halide color photographic light-sensitive material according to claim 1.
(A) It has a silver halide tabular host grain portion whose main plane is the (111) plane, and (b) at least one epitaxial is bonded to the corner portion of the host grain portion.
(C) When the epitaxial is divided into a portion (A1) projecting outward from the tabular host grain portion and a portion (A2) not projecting when viewed from the direction perpendicular to the main plane of the tabular host grain Further, the average Cl content of epitaxial corresponding to A1 part is 70% or more, and the average Cl content of epitaxial corresponding to A2 part is 60% or less. The silver halide color photographic light-sensitive material according to claim 1 or 2, comprising the following compound (A):
Compound (A): a heterocyclic compound having one or more heteroatoms, and a compound that increases the sensitivity of the silver halide color photographic light-sensitive material by adding the compound and not by adding it   The compound according to any one of claims 1 to 3, wherein the compound of type 1 or type 2 is a compound having at least one adsorbing group for silver halide or a partial structure of spectral sensitizing dye in the molecule. 2. A silver halide color photographic light-sensitive material as described in 1 above.

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