JP2005208393A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in sensitivity and graininess, and ensuring small static fog and small radiation fog. <P>SOLUTION: The silver halide color photographic sensitive material has on a support at least one each of blue-, green- and red-sensitive layers and at least one non-photosensitive layer, wherein at least one of the layers contains the following compound (A) or compound (B) and a spectral sensitivity distribution S<SB>B</SB>(λ) of the blue-sensitive layer satisfies a relationship of the expression (1): S<SB>B</SB>(370 nm)/S<SB>B</SB>(420 nm)<0.7. Compound (A): a heterocyclic compound which has one or two hetero atoms and substantially increases the sensitivity of the silver halide photographic sensitive material when added. Compound (B): a heterocyclic compound which has ≥3 hetero atoms, substantially increases the sensitivity of the silver halide photographic sensitive material when added, and does not react with an oxidized developing agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide color photosensitive material. More specifically, the present invention relates to a silver halide color photosensitive material having high sensitivity and excellent graininess.

  In the field of silver halide color photographic light-sensitive materials, it has been a long-standing problem to increase the sensitivity without impairing the graininess. In general, the photographic speed is determined by the size of the silver halide emulsion grains. The larger the emulsion grains, the higher the photographic sensitivity. However, since the graininess deteriorates with an increase in the size of silver halide grains, sensitivity and graininess are in a trade-off relationship. Increasing the sensitivity without deteriorating the graininess in the industry is the most fundamental and important issue in improving the image quality of a photographic photosensitive material. Patent Document 1 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. . Patent Document 2 discloses a technique for increasing sensitivity without deteriorating graininess.

  However, the silver halide photographic light-sensitive material whose sensitivity has been increased by the method described in the above-mentioned patent document has a large radiation cover and has been desired to be improved.

  Photosensitive materials come into contact with various substances during their production, photographing, and development processing. For example, in the processing step, when the photosensitive material is wound up, the back layer formed on the back surface of the support and the surface layer may come into contact with each other. Moreover, when conveyed in the process of a process, it may contact stainless steel, a rubber roller, etc. When contacted with these materials, the surface of the photosensitive material (gelatin layer) tends to be positively charged and, in some cases, causes an unnecessary discharge, leaving an undesirable exposure mark (called a static mark) on the photosensitive material. It will be. As a method for reducing undesirable exposure traces on a photosensitive material even when unnecessary discharge occurs, it is known to use a material that controls the spectral sensitivity in the ultraviolet region for the protective layer.

One of the problems in a photographic light-sensitive material that has been sensitized with the above compound is static covering, and an improvement has been desired.
JP 2000-194085 A JP 2003-222986 A

An object of the present invention is to provide a silver halide photographic light-sensitive material that is excellent in sensitivity and graininess, has a small static covering, and a small radiation covering.
The above object has been solved by the following method.

  As a result of diligent research, the present inventors have made it possible to provide a photosensitive material having excellent sensitivity and granularity, small static covering, and small radiation covering by the following method.

[1] The substrate has at least one blue-sensitive layer, green-sensitive layer, red-sensitive layer and non-photosensitive layer, respectively, and at least one of the following compounds (A) or (B) And a spectral sensitivity distribution S _B (λ) of the blue-sensitive layer satisfies the relationship of the following formula (1):

Compound (A): a compound that is a heterocyclic compound having one or two heteroatoms, and by adding this compound, the sensitivity of the silver halide photographic material is substantially increased as compared with the case where it is not added (B): a heterocyclic compound having 3 or more heteroatoms, which is a compound which, when added, substantially increases the sensitivity of the silver halide photographic light-sensitive material as compared with the case where it is not added, and oxidative development Compound formula (1) which does not react with main drug: S _B (370 nm) / S _B (420 nm) <0.7

[2] The silver halide color photographic light-sensitive material as described in [1] above, which contains at least one fluorine-based surfactant represented by the following general formula (X) or general formula (Y).

Formula (X)

In the general formula (X), R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. A and B each independently represent a fluorine atom or a hydrogen atom. n ^B3 and n ^B4 each independently represents an integer of 4 to 8. L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. m ^B represents 0 or 1. M represents a cation.

General formula (Y)

In the general formula (Y), R ^C1 represents a substituted or unsubstituted alkyl group (wherein the substituent does not include a fluorine atom), and R ^CF represents a perfluoroalkylene group. A represents a hydrogen atom or a fluorine atom, and L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. One of Y ^C1 and Y ^C2 represents a hydrogen atom, the other represents —L ^C2 —SO ₃ M, L ^C2 represents a single bond or a substituted or unsubstituted alkylene group, and M represents a cation.

[3] At least one color-sensitive layer of the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer is composed of two or more photosensitive layers having different sensitivities, and at least one of the highest-sensitivity layers. The silver halide color photographic light-sensitive material according to [1] or [2], wherein the compound (A) or compound (B) is contained in

[4] The silver halide color photographic light-sensitive material according to any one of [1] to [3], wherein the compound (A) or (B) is contained in at least one of the non-photosensitive layers. material.

Hereinafter, the present invention will be described in detail.
First, the compounds (A) and (B) of the present invention will be described.

  In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention may be any substituent regardless of the presence or absence of substitution.

When such a substituent is W, the substituent represented by W is not particularly limited, and examples thereof include halogen atoms, alkyl groups (cycloalkyl groups, bicycloalkyl groups, tricycloalkyl groups). ), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, 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, aminocarbonyl Mino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl 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, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), other known Substituents are mentioned as examples.

  More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, which may be condensed with a benzene ring or the like, and more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-pyridinio, 1 May be a cationic heterocyclic group such as methyl-2-quinolinio.),

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2 -Tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms) Substituted or unsubstituted heterocyclic oxy group, 1- Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 7 to 30 carbon atoms) Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy having 1 to 30 carbon atoms) Groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy) An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (Preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably Is an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino , Anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl having 1 to 30 carbon atoms, an aryl, an ammonio group substituted with a heterocycle such as trimethylammonio, Triethylammonio, diphenylmethylammonio),

An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbo having 2 to 30 carbon atoms) A ruamino group, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms) A substituted or unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having 0 to 30 carbon atoms) Substituted or unsubstituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino A group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2, 3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or substituted group having 2 to 30 carbon atoms) An unsubstituted heterocyclic thio group such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N- Ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl) ,

Sulfo groups, alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl P-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms). Bonyl group, heterocyclic carbonyl group bonded to carbonyl group by substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxy Phenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m -Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, t-butoxy Carbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di- n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocycles having 3 to 30 carbon atoms) An azo group such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably Substituted or unsubstituted phosphine having 2 to 30 carbon atoms An inofin group such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, Diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a phospho group, a silyl group (preferably , C3-C30 substituted or unsubstituted silyl , For example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino), ureido group (preferably 1 carbon atom) To 30 substituted or unsubstituted ureido groups such as N, N-dimethylureido.

  In addition, two Ws can be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring or naphthalene. Ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Phenanthroline ring, thian Ren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

Among the above-described substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents include a —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group). ).

  More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

  Compound (A) used in the present invention, that is, a heterocyclic compound having one or two heteroatoms, and compound (B), that is, a heterocyclic compound having three or more heteroatoms, and an oxidized developer Each non-reacting compound is described below.

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

  In the case of a polycyclic heterocycle, all ring systems contain only one or two heteroatoms, for example, 1,3,4,6-tetraazaindene has 4 heteroatoms. It is individual 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.

  Any of these substituents may be substituted or condensed as long as it does not violate the definition of “heterocycle having 1 or 2 heteroatoms”. 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 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 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 can be preferably used. .

  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 reactivity (CRV) of the compound of the present invention with an oxidized developing agent is determined by the following method.
The evaluation light-sensitive material (A) was processed in the same manner as described in Example 1 except that the light-sensitive material (A) was exposed to white light and the processing time of the color development step was changed to 1 minute 15 seconds. The magenta density measurement and the cyan density measurement of this photosensitive material were performed, and the difference between the magenta density and the cyan density of the photosensitive material not containing the compound of the present invention was determined. In order to improve the sensitivity / granularity ratio, CRV is preferably 0.01 or less, more preferably 0.

Evaluation material (A)
(Support) Cellulose triacetate
(Emulsion layer) Em-C 1.07 g / m ² as silver
Gelatin 2.33 g / m ²
ExC-1 0.76 g / m ²
ExC-4 0.42 g / m ²
Tricresyl phosphate 0.62 g / m ²
Compound of the present invention 3.9 × 10 ⁻⁴ mol / m ²
(Protective layer)
Gelatin 2.00 g / m ²
H-1 0.33 g / m ²
B-1 (diameter 1.7 μm) 0.10 g / m ²
B-2 (diameter 1.7 μm) 0.30 g / m ²
B-3 0.10 g / m ²

  The characteristics of the emulsion Em-C used in the evaluation light-sensitive material (A) and the structural formula of each compound are shown in the column of Example 1 below.

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

In the general formula (I), Z ₁ represents a group that forms a heterocyclic ring having 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 one or two heteroatoms is particularly preferably a compound represented by the following general formula (II).

In the general formula (II), 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, the general formula (I) and the general formula (II) will be described in detail.
The heterocyclic ring formed by Z ₁ is preferably a heterocyclic ring ((aa-1) to (aa-18), (ab-1) to (ab- 29), (ac-1) to (ac-19), (ad-1) to (ad-8)), and the like are preferable. Unless these are contrary to the definition of “heterocycle having one or two heteroatoms”, these may be further substituted with a substituent (for example, the aforementioned W) or may be condensed.

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 (I) and the general formula (II) are preferably compounds suitable for the fixing methods (1) to (7) described below, 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 compounds of the present invention can contain the requisite number of necessary cations or anions when necessary to neutralize the charge of the compounds 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 (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluenesulfonate ion, p-chloro). Benzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene sulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), Examples thereof include sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and 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.

  Preferred of the compounds of the present invention are combinations of the individual preferred above (particularly combinations of the most preferred of the individual).

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

As described above, the heterocyclic compound having one or two heteroatoms according to the present invention preferably does not react with the oxidized oxidized developing agent.

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.

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

  Heterocyclic compounds with one or two heteroatoms include Edward C. Taylor, 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 (Robert C. Elderfield), “Heterocyclic Compounds” Volumes 1-6, published by John Wiley & Sons, etc. One or two heterocyclic compounds can be used. In addition, heterocyclic compounds having 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 at room temperature for 2 hours, 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.).

  Next, the compound (B) used in the present invention, that is, a compound that is a heterocyclic compound having 3 or more heteroatoms and does not react with an oxidized developer is 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.

  A heterocyclic compound having 3 or more heteroatoms does not react with the oxidized developing agent. 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- These 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 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 compounds of the present invention, Edward C. Taylor, edited by Arnold Weissberger, “The Chemistry of Heterocyclic Compounds— Series of Monographs, Volumes 1-59, published by John Wiley & Sons, edited by Robert C. Elderfield, "Hetero" Among the compounds described in “Heterocyclic Compounds” Vol. 1-6, published by John Wiley & Sons, etc., the compounds corresponding to the present invention can be used. Moreover, the compound of this invention is compoundable based on the method as described in these.

  As the substituent of the compound of the present invention described above, any substituent for obtaining a desired photographic characteristic 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 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 of the present invention is contained in a silver halide photographic light-sensitive material, it is preferably a compound that can be fixed to a specific layer during storage and diffuses at an appropriate time of photographic processing (preferably during development processing). Is used. In order to prevent and fix the compound 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, to dissociate the compound of the present invention from the oil only during development.

  The pKa of the compound of the present invention is preferably 5.5 or more, more preferably 6.0 or more and 10.0 or less, particularly preferably 6.5 or more and 8.4 or less, and most preferably 6.9 or more. This is the case of 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 of making a compound of the present invention anti-diffusion by adding a ballast group.
(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), groups using the reverse Michael type reaction described in JP-A-59-137945, JP-A-60-41034 and the like, Chem. Lett. 585 (1988), JP-A-59-218439, JP-B-5-78025, etc., groups utilizing nucleophilic reaction, groups utilizing ester bond or amide bond hydrolysis reaction, and the like. it can.

  In order to impart the above functions, the compounds of the present invention may be substituted with blocking groups that release the compounds of the present invention during 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 of the present invention, or a polymer compound of trimer or higher.

(5) A method of fixing using the compound of the present invention (solid dispersion) insoluble in water. As described in (1), the case where the compound of the present invention has a specific pKa is preferable because the compound 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 of the present invention by coexisting a polymer having a charge opposite to that of the compound 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 adsorbing and fixing the compound of the present invention to 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 of the present invention include those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. It is.

  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 the above, the method for fixing the compound 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 compound having a blocking group. And (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 simultaneously, that is, the compound of the present invention having a specific pKa and a ballast group can be most preferably used.

The compounds of the present invention can contain the requisite number of necessary cations or anions when necessary to neutralize the charge of the compounds 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.

  Preferred of the compounds of the present invention are combinations of the individual preferred above (particularly combinations of the most preferred of the individual).

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

  The compounds of the present invention may be used alone or in combination, and the number and type of compounds used can be arbitrarily selected.

  Further, the compound 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 of the present invention can be used in combination with one or a plurality of methods having an effect of increasing sensitivity or a compound having an effect of increasing sensitivity. 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. To 100 mL of a 6: 4 (mass ratio) tetrahydrofuran / water solution containing 0.01 mmol of the compound of the present invention was added 0.5 mL of 1N sodium chloride, and the mixture was stirred under a nitrogen gas atmosphere. Titrate with aqueous potassium hydroxide. 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 silver halide color photographic light-sensitive material of the present invention contains the compound represented by the compound (A) or the compound (B), and the spectral sensitivity S _B (λ) of the blue-sensitive layer has a wavelength of 370 nm. And 420 nm are expressed by the relationship of the following formula (1).
Formula (1) S _B (370 nm) / S _B (420 nm) <0.7

In the present invention, the spectral sensitivity distribution means that a silver halide color photographic light-sensitive material is subjected to spectral exposure at intervals of several nm from 350 to 700 nm, and the reciprocal of the exposure amount that gives a constant density at each wavelength after color development processing is determined for each wavelength. The sensitivity is a function of wavelength. In the present invention, the spectral sensitivity distribution S _B (λ) of the blue-sensitive layer means a sensitivity distribution giving a yellow density. The development processing conditions for obtaining the spectral sensitivity distribution may be any processing as long as it is a general color negative development processing method, but the development processing described in Example 1 of the present application is preferable.

  In the following general formula, the spectral sensitivity at any concentration may be expressed in this range, but it is preferable that the spectral sensitivity at any concentration in the concentration range Dmin + 0.3 to Dmin + 1.0 falls within the following range.

S _B (370 nm) / S _B (420 nm) <0.7
Preferably S _B (370 nm) / S _B (420 nm) <0.6
More preferably, S _B (370 nm) / S _B (420 nm) <0.5
Most preferably, S _B (370 nm) / S _B (420 nm) <0.3
It is.

  The term “radiation fog” as used in the present invention means an increase in the minimum density after development caused by irradiation of a sample with radiation. The radiation referred to here is mainly natural radiation, but may be artificially generated radiation.

As a method for intentionally irradiating radiation, for example, ⁶⁰ Co gamma rays can be used. At a distance of 1 m from the radiation source, the dose when irradiated with 37 GBq of ⁶⁰ Co gamma rays for 8 minutes and 10 seconds is 0.2R. The degree of fog rise due to radiation can be estimated from the difference between the fog density of the sample irradiated with radiation and the fog density of the unexposed sample.

  Next, the fluorine-based surfactant preferably used in the present invention will be described in detail. Examples of the fluorine-based surfactant include compounds represented by the following general formulas (X) and (Y).

  Next, the compound represented by the following general formula (X) will be described in detail.

Formula (X)

In the general formula (X), R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. A and B each independently represent a fluorine atom or a hydrogen atom. n ^B3 and n ^B4 each independently represents an integer of 4 to 8. L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. m ^B represents 0 or 1. M represents a cation.

In the general formula (X), R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. Substituent T described later can be applied as the substituent.

R ^B3 , R ^B4 and R ^B5 are preferably an alkyl group or a hydrogen atom, more preferably an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, still more preferably a methyl group or a hydrogen atom, Preferably it is a hydrogen atom.

  In the general formula (X), A and B each independently represent a fluorine atom or a hydrogen atom. A and B are preferably both fluorine atoms or both hydrogen atoms, more preferably both fluorine atoms.

In the general formula (X), n ^B3 and n ^B4 each independently represents an integer of 4 to 8. Preferably as n ^B3 and n ^B4 in integer of 4-6, and a n ^B3 = n ^B4, more preferably an integer of 4 or 6, and an n ^B3 = n ^B4, more preferably n ^B3 = n ^B4 = 4.

In the general formula (X), m ^B represents 0 or 1, both of which are likewise preferred.

In the general formula (X), L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. As the substituent, the substituent T described later can be applied.

L ^B1 and L ^B2 each preferably have 4 or less carbon atoms, and are preferably unsubstituted alkylene.

  M represents a cation, and as the cation represented by M, for example, alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions and the like are preferable. Adapted. Preferred are lithium ion, sodium ion, potassium ion and ammonium ion, and more preferred are lithium ion, sodium ion and potassium ion. More preferred is sodium ion.

  Among the compounds represented by the general formula (X), compounds represented by the following general formula (X-1) are preferable.

Formula (X-1)

In the general formula (X-1), R ^B3 , R ^B4 , R ^B5 , n ^B3 , n ^B4 , m ^B , A, B and M have the same meanings as those in the general formula (X) and are preferable. The range is the same. n ^B1 and n ^B2 each independently represent an integer of 1 to 6.

In the general formula (X-1), n ^B1 and n ^B2 each independently represents an integer of 1 to 6. n ^B1 and n ^B2 in integer of 1 to 6, and is preferably an n ^B1 = n ^B2, 2 or 3, and more preferably from ^{n B1 = n B2, n B1} = n B2 = 2 More preferably.

  Among the compounds represented by the general formula (X), a compound represented by the following general formula (X-2) is more preferable.

Formula (X-2)

In the general formula (X-2), n ^B3 , n ^B4 , m ^B and M have the same meanings as those in the general formula (X), and preferred ranges are also the same. In the general formula (X-2), n ^B1 and n ^B2 have the same ^{meanings as those} in the general formula (X-1), and preferred ranges are also the same.

  The compound represented by the general formula (X) is more preferably a compound represented by the following general formula (X-3).

Formula (X-3)

In the general formula (X-3), n ^B5 represents 2 or 3, and n ^B6 represents any integer of 4 to 6. m ^B represents 0 or 1, both of which are likewise preferred. M has the same meaning as M in the general formula (X), and the preferred range is also the same.

Specific examples of the compound represented by the general formula (X) are shown below, but the present invention is not limited to the following specific examples.

  The compound represented by the general formula (X) can be easily synthesized by combining a general esterification reaction and a sulfonation reaction. The counter cation can be easily converted with an ion exchange resin. Although the example of a typical synthesis method is given to the following, this invention is not limited at all by the following specific synthesis examples.

(Synthesis Example 1: Synthesis of FS-201)
1-1 Synthesis of maleic acid di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) Maleic anhydride 90.5 g (0.924 mol), 3,3,4,4 , 5,5,6,6,6-nonafluorohexanol 500 g (1.89 mol) and p-toluenesulfonic acid monohydrate 17.5 g (0.09 mol) in 1000 L of toluene by distilling off the water produced. The mixture was heated to reflux for 20 hours. Thereafter, the mixture was cooled to room temperature, toluene was added, the organic phase was washed with water, and the solvent was distilled off under reduced pressure to obtain 484 g (yield 86%) of the desired product as a transparent liquid.

1-2 Synthesis of FS-201 514 g (0.845 mol) of maleic acid di (3,3,4,4,5,5,6,6,6-nonafluorohexyl), 91.0 g of sodium bisulfite (0. 875 mol) and 250 mL of water-ethanol (1/1 v / v) were added and heated under reflux for 6 hours, followed by extraction with 500 mL of ethyl acetate and 120 mL of a saturated aqueous sodium chloride solution. The organic phase was recovered, sodium sulfate was added, and dehydration was performed. After removing sodium sulfate by filtration and concentrating the filtrate, 2.5 L of acetone was added and heated. The insoluble material was removed by filtration, and then cooled to 0 ° C., and 2.5 L of acetonitrile was slowly added. The precipitated solid was collected by filtration, and the obtained crystals were dried under reduced pressure at 80 ° C. to obtain 478 g (yield 79%) of the target compound as white crystals. The ¹ H-NMR data of the obtained compound is as follows.

¹ H-NMR (DMSO-d ₆ ) δ 2.49-2.62 (m, 4H), 2.85-2.99 (m, 2H), 3.68 (dd, 1H), 4.23-4 .35 (m, 4H)

  Next, the compound represented by the following general formula (Y) will be described in detail.

General formula (Y)

In the general formula (Y), R ^C1 represents a substituted or unsubstituted alkyl group (wherein the substituent does not include a fluorine atom), and R ^CF represents a perfluoroalkylene group. A represents a hydrogen atom or a fluorine atom, and L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. One of Y ^C1 and Y ^C2 represents a hydrogen atom, the other represents —L ^C2 —SO ₃ M, L ^C2 represents a single bond or a substituted or unsubstituted alkylene group, and M represents a cation.

In the general formula (Y), R ^C1 represents a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group represented by R ^C1 may be linear, branched, or have a cyclic structure. Substituent T described later can be applied as the substituent. Preferred examples of the substituent include alkenyl groups, aryl groups, alkoxy groups, halogen atoms (preferably Cl), carboxylic acid ester groups, carbonamido groups, carbamoyl groups, oxycarbonyl groups, and phosphoric acid ester groups.

R ^C1 is preferably an unsubstituted alkyl group, R ^C1 is more preferably an unsubstituted alkyl group having 2 to 24 carbon atoms, still more preferably an unsubstituted alkyl group having 4 to 20 carbon atoms, and particularly preferably Is an unsubstituted alkyl group having 6 to 24 carbon atoms.

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

  A represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent group formed by combining these. The substituent is the same as the preferred range of the substituent mentioned for R ^C1 . L ^C1 preferably has 4 or less carbon atoms, and is preferably unsubstituted alkylene.

One of Y ^C1 and Y ^C2 represents a hydrogen atom, the other represents -L ^C2 -SO ₃ M, and M represents a cation. Here, preferable examples of the cation represented by M include alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions, and the like. . Of these, more preferably lithium ion, sodium ion, potassium ion or ammonium ion, still more preferably lithium ion, sodium ion or potassium ion, and the total number of carbon atoms and substituents of the compound of the general formula (Y). The alkyl group can be appropriately selected depending on the degree of branching of the alkyl group. When the total number of carbon atoms of R ^C1 , R ^CF and L ^C1 is 16 or more, lithium ions are excellent in terms of compatibility between solubility (particularly against water) and antistatic ability or coating uniformity. .

L ^C2 represents a single bond or a substituted or unsubstituted alkylene group. The substituent is the same as the preferred range of the substituent mentioned for R ^C1 .

L ^C2 is preferably a single bond or an alkylene group having 2 or less carbon atoms, more preferably a single bond or an unsubstituted alkylene group, and still more preferably a single bond or a methylene group. L ^C2 is particularly preferably a single bond.

  Among the compounds represented by the general formula (Y), a compound represented by the following general formula (Y-1) is preferable.

General formula (Y-1)

In the general formula (Y-1), R ^C11 represents a substituted or unsubstituted alkyl group having 6 or more carbon atoms in total. R ^CF1 represents a perfluoroalkyl group having 6 or less carbon atoms. One of Y ^C11 and Y ^C12 represents a hydrogen atom, the other represents SO ₃ M ^C , and M ^C represents a cation. n ^C1 represents an integer of 1 or more.

In the general formula (Y-1), R ^C11 represents a substituted or unsubstituted alkyl group having a total carbon number of 6 or more. However, R ^C11 does not become an alkyl group substituted with a fluorine atom. The substituted or unsubstituted alkyl group represented by R ^C11 may be linear, branched, or have a cyclic structure. Examples of the substituent include alkenyl groups, aryl groups, alkoxy groups, halogen atoms other than fluorine, carboxylic acid ester groups, carbonamido groups, carbamoyl groups, oxycarbonyl groups, and phosphoric acid ester groups.

The substituted or unsubstituted alkyl group represented by R ^C11 preferably has 6 to 24 carbon atoms in total. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group (2EH), n-nonyl group, 1 1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2 -A decyl tetradecyl group, a tricosyl group, a cyclohexyl group, a cycloheptyl group, etc. are mentioned. In addition, preferable examples of the substituted alkyl group having 6 to 24 carbon atoms including the carbon atoms of the substituent include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group, 2- Methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12- (p-chlorophenyl) dodecyl group, 2- (diphenyl phosphate) An ethyl group etc. can be mentioned.

The substituted or unsubstituted alkyl group represented by R ^C11 preferably has a total carbon number of 6 to 18. Preferred examples of the unsubstituted alkyl group having 6 to 18 carbon atoms include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3- Examples include trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like. In addition, preferable examples of the substituted alkyl group having 6 to 18 carbon atoms in total including the carbon number of the substituent include phenethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, oleyl group, linoleyl group, linolenyl group and the like. Is mentioned. Among them, as R ^C11 , n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, It is more preferably n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, oleyl group, linoleyl group, linolenyl group, and linear, cyclic or branched unsubstituted having 8 to 16 carbon atoms. Particularly preferred is an alkyl group.

In the general formula (Y-1), R ^CF1 represents a perfluoroalkyl group having 6 or less carbon atoms. Here, the perfluoroalkyl group refers to a group in which all hydrogen atoms of the alkyl group are substituted with fluorine. The alkyl group in the perfluoroalkyl group may be linear or branched, and may have a cyclic structure. Examples of the perfluoroalkyl group represented by R ^CF1 include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group, undecafluoro-n. -Pentyl group, tridecafluoro-n-hexyl group, undecafluorocyclohexyl group and the like. Among these, a perfluoroalkyl group having 2 to 4 carbon atoms (for example, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, a nonafluoro-n-butyl group, etc.) is preferable, and heptafluoro-n-propyl. The group, nonafluoro-n-butyl group is particularly preferred.

In the general formula (Y-1), n ^C1 represents an integer of 1 or more. Preferably, it is an integer of 1 to 4, and particularly preferably 1 or 2.

Further, as a combination of n ^C1 and R ^CF1 , when n ^C1 = 1, R ^CF1 is a heptafluoro-n-propyl group or a nonafluoro-n-butyl group; when n ^C1 = 2, R ^CF1 is nonafluoro- More preferably, it is an n-butyl group.

In the general formula (Y-1), Y ^C11 and Y ^C12 is a hydrogen atom while the other represents SO ₃ M ^C, M ^C represents a cation. Examples of the cation represented by M ^C, for example, an alkali metal ion (lithium ion, sodium ion, potassium ion), alkaline earth metal ions (barium ion, calcium ion, etc.), an ammonium ion and the like are preferably exemplified The Of these, lithium ions, sodium ions, potassium ions or ammonium ions are particularly preferred, and sodium ions are most preferred.

Specific examples of the compound represented by the general formula (Y) are shown below, but the present invention is not limited to the following specific examples.

  The compound represented by the above general formula (Y) can be easily synthesized by performing a monoesterification reaction, an acid halogenation, an esterification reaction, and a sulfonation reaction in this order using general maleic anhydride as a raw material. is there. The counter cation can be easily converted with an ion exchange resin.

  Although the example of a typical synthesis method is given to the following, this invention is not limited at all by the following specific synthesis examples.

(Synthesis Example 2: Synthesis of FS-303)
2-1 Synthesis of maleic acid (2-ethylhexyl) chloride While maintaining 4.1 g (20 mmol) of phosphorus pentachloride with 4.5 g (20 mmol) of mono (2-ethylhexyl) maleate manufactured by Aldrich at 30 ° C. or lower. It was dripped slowly. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Then, it heated at 60 degreeC, pressure-reduced with the aspirator, the produced | generated phosphorus oxychloride was distilled off, and 4.5g (yield 92%) of brown oily compound maleic acid (2-ethylhexyl) chloride was obtained.

2-2 Synthesis of mono-2-ethylhexyl maleate mono 2,2,3,3,4,4,4-heptafluorobutyl 66.8 g of 2,2,3,3,4,4,4-heptafluorobutanol ( 0.334 mol) and 29.6 mL (0.367 mol) of pyridine are dissolved in 180 mL of acetonitrile, cooled in an ice bath, and maintained at an internal temperature of 20 ° C. or less, 90.6 g (0. 367 mol) was added dropwise. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereafter, 1000 mL of ethyl acetate was added, and the organic phase was washed with a 1 mol / L hydrochloric acid aqueous solution and a saturated sodium chloride aqueous solution. Then, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10 / (0-7 / 3 v / v), purification operation was performed to obtain 80.3 g (yield 59%) of the target compound as a colorless transparent oily compound.

2-3 Synthesis of cidium mono 2-ethylhexyl mono 2,2,3,3,4,4,4-heptafluorobutyl sulfosuccinate (FS-302) Maleic acid mono 2-ethylhexyl mono 2,2,3,3 , 4,4,4-heptafluorobutyl 80.3 g (0.196 mol), sodium bisulfite 20.4 g (0.196 mol), 80 ml of water-ethanol (1/1 v / v) were added and heated to reflux for 10 hours. . Thereafter, 1000 mL of ethyl acetate was added, and the organic phase was washed with a saturated aqueous solution of sodium chloride. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (chloroform / methanol: 9/1 v / v). After purifying and washing the recovered organic phase with a saturated aqueous sodium chloride solution, the organic solvent was distilled off under reduced pressure to obtain 32 g (yield 32%) of the target compound as a colorless transparent solid.

The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d) δ 0.81-0.87 (m, 6H), 1.24 (m, 8H), 1.50 (br, 1H), 2.77-2.99 (m, 2H), 3.63-3.71 (m, 1H), 3.86-3.98 (m, 3H), 4.62-4.84 (br, 1H)

(Synthesis Example 3: Synthesis of FS-312)
3-1 Synthesis of monodecyl maleate mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl 3,3,4,4,5,5,6,6,6-nonafluoro 164.6 g (623 mmol) of hexanol and 49.3 mL (623 mmol) of pyridine were dissolved in 280 mL of chloroform, cooled in an ice bath, and 155.8 g (566 mmol) of monododecyl chloride maleate were added dropwise while maintaining the internal temperature at 20 ° C. or lower. . After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereafter, ethyl acetate was added, and the organic phase was washed with a 1 mol / L aqueous hydrochloric acid solution and a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 -7/3 v / v), and 48.2 g (yield 18%) of the target compound was obtained.

3-2 Synthesis of sodium monodecyl mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl sulfosuccinate (FS-312) Monodecyl maleate mono 3,3,4,4,5 5,6,6,6-Nonafluorohexyl 48.0 g (90 mmol), sodium hydrogen sulfite 10.4 g (99 mmol), and water-ethanol (1/1 v / v) 50 mL were added and heated under reflux for 5 hours. Thereafter, ethyl acetate was added, and the organic phase was washed with a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and recrystallization was performed with acetonitrile. 12.5 g (yield 22%) of the target compound was obtained as a colorless transparent solid.

The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d) δ 0.81-0.87 (t, 3H), 1.24 (m, 18H), 1.51 (br, 2H), 2.50-2.70 (m, 2H), 2.70-2.95 (m, 2H), 3.61-3.70 (m, 1H), 3.96 (m, 2H), 4.28 (ms, 2H)

(Synthesis Example 4: Synthesis of FS-309)
4-1 Synthesis of mono-2-ethylhexyl maleate mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl 3,3,4,4,5,5,6,6,6 -515 g (1.95 mol) of nonafluorohexanol, 169 g (2.13 mol) of pyridine, 394 mL (3.89 mol) of triethylamine were dissolved in 1000 mL of chloroform, cooled in an ice bath, and maleic acid ( 530 g (2.14 mol) of 2-ethylhexyl) chloride was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. Thereafter, chloroform was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 to 7/3 v / The purification operation was performed in v) to obtain 508 g (yield 50%) of the colorless and transparent target compound.

4-2 Synthesis of sodium (mono-2-ethylhexyl) (mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl) sulfosuccinate (FS-309) Maleic acid (mono-2- Ethyl hexyl) (mono 3,3,4,4,5,5,6,6,6-nonafluorohexyl) 137.5 g (0.29 mol), sodium hydrogen sulfite 33.2 g (0.32 mol), water-ethanol (1/1 v / v) 140 mL was added and heated to reflux for 2 hours. Thereafter, 1000 mL of ethyl acetate was added, and the organic phase was washed with a saturated aqueous solution of sodium chloride. Then, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, recrystallization operation was performed with 800 mL of toluene, and crystals were formed by cooling in an ice bath. Precipitated. Finally, the crystals were separated by filtration to obtain 140 g (yield 84%) of a colorless and transparent target compound.

¹ H-NMR (DMSO-d ₆ ) δ 0.82-0.93 (m, 6H), 1.13-1.32 (m, 8H), 1.50 (br, 1H), 2.57-2 .65 (m, 2H), 2.84-2.98 (m, 2H), 3.63-3.68 (m, 1H), 3.90 (d, 2H), 4.30 (m, 2H) )

(Synthesis Example 5: Synthesis of FS-332)
5-1 Synthesis of mono-2-ethylhexyl maleate mono (1,1,1,3,3,3-hexafluoro-2-propyl) 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) 33.7 g (201 mmol) and pyridine 17.9 mL (220 mmol) were dissolved in acetonitrile 80 mL, cooled in an ice bath, and maintained at an internal temperature of 20 ° C. or lower, 41.8 g (220 mmol) of mono-2-ethylhexyl chloride maleate. ) Added dropwise. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Thereafter, ethyl acetate was added, and the organic phase was washed with a 1 mol / L aqueous hydrochloric acid solution and a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / chloroform: 10/0 (7/3 v / v), and 10.6 g (yield 14%) of the target compound was obtained as a colorless transparent oily compound.

5-2 Synthesis of FS-332 Mono-2-ethylhexyl maleate (1,1,1,3,3,3-hexafluoro-2-propyl) 10.6 g (28 mmol), sodium bisulfite 3.2 g (31 mmol) ), 10 mL of water-ethanol (1/1 v / v) was added and heated to reflux for 10 hours. Thereafter, ethyl acetate was added, and the organic phase was washed with a saturated aqueous sodium chloride solution. The organic layer was recovered, the organic solvent was distilled off under reduced pressure, and recrystallization was performed with acetonitrile. 1.7 g (yield 13%) of the target compound was obtained as a colorless and transparent solid.

The ¹ H-NMR data of the obtained compound is as follows.
¹ H-NMR (DMSO-d) δ 0.81-0.87 (m, 6H), 1.25 (m, 8H), 1.50 (br, 1H), 2.73-2.85 (m, 2H), 3.59 (m, 1H), 3.85-3.90 (m, 2H), 12.23 (br, 1H)

  Of the various compounds described above, ionic surfactants are used in various different salt forms by means of ion exchange or neutralization, etc., depending on the purpose of use, various properties required, etc. It can be used in the presence of two or more counter ions.

  There are no particular restrictions on the use layer / amount of the fluorine compound of the present invention, and the amount used depends on the structure and use of the compound used, the type and amount of the material contained in the aqueous composition, and the composition of the medium. Can be arbitrarily determined. For example, when the aqueous coating composition of the present invention is used as a coating solution for the uppermost hydrophilic colloid (gelatin) layer of a silver halide photographic light-sensitive material, the concentration of the fluorine compound of the present invention in the coating composition is 0. 0.003 to 0.5 mass% is preferable, and 0.03 to 5 mass% is preferable with respect to gelatin solid content.

  Hereinafter, examples of the substituent which the substitutable group in the above general formula may have and the substituent T will be described.

  Examples of the substituent T include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Examples thereof include a methyl group, an ethyl group, and isopropyl. Group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably). Is an alkenyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group, and an alkynyl group (preferably a carbon atom). An alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a propargyl group, 3 A pentynyl group), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as a phenyl group and p-methyl group). A phenyl group, a naphthyl group, etc.), a substituted or unsubstituted amino group (preferably a carbon number of 0-20, more preferably a carbon number of 0-10, particularly preferably a carbon number of 0-6, For example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group and the like, an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably Is an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group), an aryloxy group (preferably Or an aryloxy group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group), acyl Group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 to 12 carbon atoms, and examples thereof include acetyl group, benzoyl group, formyl group, and pivaloyl group) An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably Is an aryloxycarbonyl group having 7 to 10 carbon atoms, such as a phenyloxycarbonyl group, and an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably carbon atoms). An acyloxy group having 2 to 10 carbon atoms, such as an acetoxy group and a benzoyloxy group, and an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 carbon atoms). 10 to 10 acylamino groups such as acetylamino group and benzoylamino group), alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 carbon atoms). To 12 alkoxycarbonylamino groups, such as methoxycarbonylamino group, etc. Mentioned are),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group) A sulfonylamino group (preferably a sulfonylamino group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as a methanesulfonylamino group and a benzenesulfonylamino group. A sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as a sulfamoyl group and a methylsulfamoyl group. Dimethylsulfamoyl group, phenylsulfamoyl group, etc. A carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as an unsubstituted carbamoyl group, a methylcarbamoyl group, A diethylcarbamoyl group, a phenylcarbamoyl group, etc.), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Group, an ethylthio group, etc.), an arylthio group (preferably an arylthio group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group) ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to carbon atoms). 6, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly A sulfinyl group having 1 to 12 carbon atoms is preferable, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group, and a ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferable). Is a ureido group having 1 to 12 carbon atoms, and examples thereof include an unsubstituted ureido group, a methylureido group, and a phenylureido group, and a phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably carbon. A phosphoric acid amide group having 1 to 16, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide group and phenylphosphoric acid Amide group etc.), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, A hydrazino group, an imino group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, oxygen atom, sulfur atom, etc. For example, imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 carbon atoms) To 40, more preferably 3 to 30 carbon atoms, particularly preferably a silyl group having 3 to 24 carbon atoms. If, trimethylsilyl group, etc. triphenylsilyl group), and the like. These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

  Next, silver halide crystals that are preferably used in the light-sensitive material of the present invention will be described.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide.
Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. Those having crystal defects of the above, or a composite form thereof may be used.
The silver halide grains may be fine grains having a size of about 0.2 μm or less or large size grains having a projected area diameter of about 10 μm, and the emulsion may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22-23, I. Emulsion preparation and types, and No. 18716 (November 1979), 648, No. 307105 (November 1989), 863-865, and Grafkide's "Physics and Chemistry of Photography", published by Paul Monter (P. Glafkides, Chimie et Phisique Photographiques, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions", Focal It can be prepared using a method described in Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 164).
Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and GB 1,413,748 are also preferred.

Tabular grains having an aspect ratio of about 3 or more are particularly preferred and can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048. , No. 4,439,520 and GB 2,112,157.
When used in the high sensitivity layer, tabular grains having an average aspect ratio of 8 or more are particularly preferable. The average aspect ratio is preferably 8 or more and 100 or less, and more preferably 12 or more and 50 or less.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.

The above emulsion preferably has dislocations. In particular, tabular grains preferably have dislocations in the fringes. As a method for introducing the dislocation, there can be used a method in which an aqueous solution of alkali iodide or the like is added to form a high silver iodide layer, a method in which AgI fine particles are added, a method described in JP-A-5-323487, and the like. .
The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such a process are described in RD No. 17643, No. 18716 and No. 307105, and the corresponding parts are summarized in the following table.
In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

  Photosensitive silver halide grains with fogged surface as described in US Pat. No. 4,082,553, silver halide grains with fogged inside as described in US Pat. No. 4,626,498, JP-A-59-214852, and colloidal silver. It is preferably applied to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of whether the photosensitive material is unexposed or exposed. The preparation method thereof is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver bromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain mass or number of grains has a grain size within ± 40% of the average grain size). Are preferred).

  Next, the structure of the silver halide photographic material preferably used in the present invention will be described.

  The color light-sensitive material of the present invention has at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer and non-light-sensitive layer on the support.

  In a multilayer silver halide color photographic light-sensitive material, generally, an arrangement of unit light-sensitive layers is arranged in the order of a red color-sensitive layer, a green color-sensitive layer, and a blue color sensitivity in order 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 sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer is a high-sensitivity emulsion layer as described in German Patent 1,121,470 or British Patent 923,045. The two low-sensitivity emulsion layers are preferably arranged so that the photosensitivity decreases sequentially toward the support. 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, 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 / RH It can be installed in the order of.

  Further, as described in JP-B-55-34932, the light-sensitive layer 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 Nos. 56-25738 and 62-63936, they can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH 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.

It is preferable to use an interlayer suppression effect as a means for improving color reproducibility.
In addition, it is also preferable to coat a donor layer that gives a multilayer effect to the red-sensitive layer. That is, the centroid sensitivity wavelength λ _G of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm <λ _G ≦ 580 nm and the red-sensitive silver halide emulsion layer is in the range of 500 nm to 600 nm. The center-of-gravity wavelength (λ _−R ) of the spectral sensitivity distribution of the magnitude of the multilayer effect received from the emulsion layer is 500 nm <λ _−R <560 nm, and λ _G −λ _−R is 5 nm or more, preferably 10 nm or more. It is preferable.

In the formula, S _G (λ) is a spectral sensitivity distribution curve of the green-sensitive silver halide emulsion layer, and S _R at a specific wavelength λ has a magenta density of +0.5 when exposure is performed at a specific wavelength. It is expressed by the reciprocal of the exposure amount.

  In order to give a multilayer effect to the red-sensitive layer as described above in a specific wavelength range, it is preferable to separately provide a multilayer effect donor layer containing silver halide grains that are spectrally sensitized. In order to realize the spectral sensitivity of the present invention, the center-of-gravity sensitivity wavelength of the multi-layered donor layer is preferably set to 510 nm to 540 nm.

Here, the gravity center wavelength λ _-R of the wavelength distribution of the magnitude of the multi-layer effect that the red-sensitive silver halide emulsion layer receives from other silver halide emulsion layers in the range of 500 nm to 600 nm is disclosed in Japanese Patent Publication No. 3-10287. It can be determined by the method described.

In the present invention, the center of gravity wavelength λ _R of the red color sensitive layer is preferably 630 nm or less. Here, the center-of-gravity wavelength λ _R of the red color-sensitive layer is defined by the formula (I).

In the equation, S _R (λ) is a spectral sensitivity distribution curve of the red color-sensitive layer, and S _R at a specific wavelength λ is an exposure amount at which the cyan density becomes fog + 0.5 when exposure at a specific wavelength is given. It is expressed as an inverse number.

  Further, as a material that gives the multi-layer effect, a compound that reacts with an oxidation product of a developing agent obtained by development and releases a development inhibitor or a precursor thereof is used. For example, a DIR (development inhibitor releasing type) coupler, a DIR-hydroquinone, a DIR-hydroquinone, or a coupler that releases a precursor thereof is used. In the case of a highly diffusible development inhibitor, the development suppression effect can be obtained wherever this donor layer is positioned in the multilayer structure, but this is also corrected because it also causes an unintended development suppression effect. In order to achieve this, it is preferable to cause the donor layer to develop color (for example, to develop the same color as the layer affected by an undesirable development inhibitor). In order to obtain the desired spectral sensitivity of the light-sensitive material of the present invention, it is preferable that the donor layer giving the multilayer effect develops magenta color.

The silver halide grains used for the layer that gives the red layer a multi-layer effect are not particularly limited in size and shape, for example, but so-called tabular grains having a high aspect ratio, monodispersed emulsions having a uniform grain size, iodine Silver iodobromide grains having a layered structure are preferably used. In order to enlarge the exposure latitude, it is preferable to mix two or more emulsions having different grain sizes.
The donor layer that gives a multilayer effect to the red sensitive layer may be applied at any position on the support, but it may be applied closer to the support than the blue sensitive layer and farther from the support than the red sensitive layer. preferable. More preferably, it is closer to the support than the yellow filter layer.

  The donor layer that gives a multilayer effect to the red-sensitive layer is closer to the support than the green-sensitive layer, more preferably farther from the support than the red-sensitive layer, and adjacent to the side closer to the support of the green-sensitive layer. It is most preferable to be located. In this case, “adjacent” means that no intermediate layer or the like is interposed therebetween.

The layer that gives the red layer a multi-layer effect may be composed of a plurality of layers. In that case, the positions may be adjacent to each other or separated from each other.
In the present invention, solid disperse dyes described in JP-A-11-305396 can be used.

Various additives can be used in the silver halide photographic light-sensitive material of the present invention depending on the purpose.
These additives are described in more detail in Research Disclosure (RD) Item 17643 (December 1978), Item 18716 (November 1979), and Item 308119 (December 1989). Are summarized below.

Additive type RD17643 RD18716 RD308119
1 Chemical sensitizer 23 pages 648 right column 996 pages 2 Sensitivity enhancers Same as above 3 Spectral sensitizers 23 to 24 pages 648 right columns 649 pages 996 right columns 998 pages right Supersensitizers right Column Column 4 Whitening agent Page 24 998 Right column 5 Antifoggant 24-25 Page 649 Right column 998 Right column-1000 and Stabilizer Right column 6 Light absorber, P. 25-26 Page 649 Right column ~ 650 page 1003 left column ~ page 1003 Luther dye, left column right column UV absorber 7 stain inhibitor page 25 right column page 650 left column to right column page 1002 right column 8 dye image stabilizer 25 page 1002 right column 9 Hardener page 26 page 651 left column page 1004 right column-page 1005
Left column
10 Binder page 26 Same as above page 1003 right column to page 1004
Right column
11 Plasticizer, Lubricant page 27 page 650 right column page 1006 left column to page 1006
Right column
12 Coating aid, surface 26-27 Same as above 1005 left column-1006 activator left column
13 Static prevention page 27 Same as above Page 1006, right column to page 1007 Agent left column
14 Matting agent page 1008 left column to page 1009
Left column

  In addition, techniques such as layer arrangement that can be used in the silver halide photographic light-sensitive material of the present invention, functional couplers such as silver halide emulsions, dye-forming couplers, and DIR couplers, various additives, and development processing Is described in the specification of European Patent Application No. 056596A1 (published on Oct. 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding location.

1. Layer structure: 61 pages 23-35 lines, 61 pages 41 lines-62 pages 14 lines Middle layer: 61 pages 36-40 lines,
3. Multilayer effect imparting layer: 62 pages 15-18 lines,
4). Silver halide halogen composition: 62 pages 21-25,
5). Silver halide grain habit: page 62 lines 26-30,
6). Silver halide grain size: 62 pages 31-34,
7). Emulsion production method: 62 pages 35-40 lines,
8). Silver halide grain size distribution: page 62, lines 41-42,
9. Tabular grains: 62 pages 43-46,
Ten. Internal structure of particles: 62 pages 47 lines to 53 lines,
11． Emulsion latent image formation type: 62 pages 54 lines-63 pages 5 lines,
12． Emulsion physical ripening / chemical ripening: p. 63, lines 6-9,
13. Mixed use of emulsion: page 63, lines 10-13,
14. Kabaze emulsion: p. 63, lines 14-31,
15． Non-photosensitive emulsion: p. 63, lines 32-43,
16． Amount of coated silver: 63 pages 49-50 lines,
17． Formaldehyde scavenger: page 64 lines 54-57,
18． Mercapto-type antifoggant: page 65, line 1-2,
19. Release agent such as fogging agent: page 65, lines 3-7,
20． Dye: 65 pages 7-10 lines,
twenty one. Color coupler in general: page 65, lines 11-13,
twenty two. Yellow, magenta and cyan couplers: 65 pages 14-25,
twenty three. Polymer coupler: page 65, lines 26-28,
twenty four. Diffusible dye-forming coupler: page 65, lines 29-31,
twenty five. Colored coupler: 65 pages 32-38 lines,
26. Functional couplers in general: 65 pages 39-44,
27. Bleach accelerator releasing coupler: 65 pages 45-48,
28. Development accelerator releasing coupler: page 65, lines 49-53,
29. Other DIR couplers: 65 pages 54 lines-66 pages 4 lines,
30. Coupler dispersion method: page 66, line 5-28,
31. Preservatives and fungicides: 66 pages 29-33,
32. Type of sensitive material: 66 page 34-36,
33. Photosensitive layer thickness and swelling speed: 66 pages 40 lines-67 pages 1 line,
34. Back layer: 67 pages 3-8 lines,
35. Development processing in general: page 67, lines 9-11,
36. Developer and developer: p. 67, lines 12-30,
37. Developer additive: p. 67, lines 31-44,
38. Inversion processing: 67 pages 45-56 lines,
39. Treatment liquid opening ratio: 67 pages 57 lines-68 pages 12 lines,
40. Development time: 68 pages, lines 13-15,
41. Bleach fixing, bleaching, fixing: 68 pages 16 lines-69 pages 31 lines,
42. Automatic processor: Page 69, lines 32-40,
43. Washing, rinsing, stabilization: 69 pages 41 lines-70 pages 18 lines,
44. Treatment liquid replenishment, reuse: page 70, lines 19-23,
45. Photosensitive material with developer: page 70, lines 24-33,
46. Development temperature: page 70, lines 34-38,
47. Use for lens-equipped film: page 70, lines 39-41

  Further, regarding the bleaching solution, magnetic recording layer, polyester support, antistatic agent, etc. that can be used in the silver halide photographic light-sensitive material of the present invention, and the use for the advanced photo system of the present invention, etc. US Patent Application Publication No. 2002 / 0042030A1 (published on April 11, 2002) and the patents cited therein. The following is a list of each item and the corresponding location.

1. Bleaching solution: page 15 [0206],
2. Magnetic recording layer and magnetic particles: page 16 [0207]-[0213],
3. Polyester support: page 16 [0214] to page 17 [0218],
4). Antistatic agent: page 17 [0219]-[0221],
5). Slip agent: page 17 [0222],
6). Matting agent: 17 pages [0224],
7). Film cartridge: page 17 [0225] to page 18 [0227],
8). Use for Advanced Photo System: 18 pages [0228], [0238]-[0240],
9. Use for film with lens: page 18 [0229]
Ten. Processing in the minilab system: page 18 [0230]-[0237]

Examples of the present invention are shown below. However, the present invention is not limited to this example.
<Example 1>
Silver halide emulsions Em-A to Em-O described in Table 1 were prepared with reference to the method for producing Em-A to Em-O described in Example 1 of JP-A-2001-281815. At that time, the sensitizing dye used in the corresponding emulsion was the same as that used in each emulsion described in Example 1 of JP-A-2001-281815.

  In Table 1, dislocation lines as described in JP-A-3-237450 are observed for tabular grains when a high-voltage electron microscope is used.

(Preparation of sample 101)
Each layer having the following composition was coated on a triacetyl cellulose support to form a color negative film (sample 101).

(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 organic solvent ExY: Yellow coupler H: Gelatin hardener (Specific compounds are described below, followed by a numerical value, followed by a symbol, The chemical formula is mentioned).
The numbers corresponding to each component indicate 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 0.127
Silver iodobromide emulsion Silver 0.008
(Average sphere equivalent diameter 0.07μm, silver iodide content 2mol%)
Gelatin 0.900
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.005
HBS-2 0.002
F-8 0.001

Second layer (second antihalation layer)
Black colloidal silver Silver 0.019
Gelatin 0.425
ExF-1 0.002
Solid disperse dye ExF-9 0.120
HBS-1 0.074
F-8 0.001

Third layer (intermediate layer)
Cpd-1 0.080
HBS-1 0.042
Gelatin 0.300

Fourth layer (low sensitivity red sensitive emulsion layer)
Em-D Silver 0.407
Em-C Silver 0.457
ExC-1 0.233
ExC-2 0.026
ExC-3 0.129
ExC-4 0.155
ExC-5 0.029
ExC-6 0.013
Cpd-2 0.025
Cpd-4 0.025
ExC-8 0.050
HBS-1 0.114
HBS-5 0.038
Gelatin 1.474

5th layer (medium sensitivity red sensitive emulsion layer)
Em-B Silver 0.601
Em-C Silver 0.301
ExC-1 0.154
ExC-2 0.037
ExC-3 0.018
ExC-4 0.103
ExC-5 0.037
ExC-6 0.050
Cpd-2 0.036
Cpd-4 0.028
Cpd-6 0.060
ExC-7 0.010
HBS-1 0.129
Gelatin 1.086

6th layer (high sensitivity red sensitive emulsion layer)
Em-A Silver 0.950
ExC-1 0.072
ExC-3 0.035
ExC-10 0.080
Cpd-2 0.064
Cpd-4 0.077
Cpd-6 0.060
ExC-7 0.040
ExM-5 0.010
HBS-1 0.329
HBS-2 0.120
Gelatin 1.245

7th layer (intermediate layer)
Cpd-1 0.094
Cpd-7 0.369
Solid disperse dye ExF-4 0.030
HBS-1 0.049
Polyethyl acrylate latex 0.088
Gelatin 0.886

Eighth layer (a layer that gives a layered effect to the red sensitive layer)
Em-J Silver 0.300
Em-K Silver 0.200
Cpd-4 0.030
ExM-2 0.057
ExM-3 0.016
ExM-4 0.051
ExY-1 0.008
ExY-6 0.042
ExC-9 0.011
HBS-1 0.090
HBS-3 0.003
HBS-5 0.030
Gelatin 0.610

9th layer (low sensitivity green sensitive emulsion layer)
Em-H Silver 0.200
Em-G Silver 0.220
Em-I Silver 0.130
ExM-2 0.378
ExM-3 0.047
ExY-1 0.009
ExC-9 0.007
HBS-1 0.098
HBS-3 0.010
HBS-4 0.077
HBS-5 0.548
Cpd-5 0.010
Gelatin 1.470

10th layer (medium sensitive green sensitive emulsion layer)
Em-F Silver 0.536
ExM-2 0.049
ExM-3 0.035
ExM-4 0.014
ExY-1 0.003
ExY-5 0.006
ExC-6 0.007
ExC-8 0.010
ExC-9 0.012
HBS-1 0.065
HBS-3 0.002
HBS-5 0.020
Cpd-5 0.004
Gelatin 0.446

11th layer (High sensitivity green sensitive emulsion layer)
Em-E silver 0.493
Em-G Silver 0.440
ExC-7 0.010
ExM-1 0.022
ExM-2 0.045
ExM-3 0.014
ExM-4 0.010
ExM-5 0.010
Cpd-3 0.004
Cpd-4 0.007
Cpd-5 0.010
HBS-1 0.148
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.939

12th layer (yellow filter layer)
Cpd-1 0.094
Solid disperse dye ExF-2 0.150
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-7 0.010
HBS-1 0.049
Gelatin 0.630

13th layer (low sensitivity blue sensitive emulsion layer)
Em-O Silver 0.060
Em-M Silver 0.404
Em-N Silver 0.076
ExC-1 0.048
ExY-1 0.012
ExY-2 0.350
ExY-6 0.060
ExY-7 0.300
ExC-9 0.012
Cpd-2 0.100
Cpd-3 0.004
HBS-1 0.222
HBS-5 0.074
Gelatin 2.058

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-L Silver 0.974
ExY-2 0.100
ExY-7 0.100
Cpd-2 0.075
Cpd-3 0.001
HBS-1 0.071
Gelatin 0.678

15th layer (first protective layer)
Silver iodobromide emulsion Silver 0.280
(Average sphere equivalent diameter 0.07μm, silver iodide content 2mol%)
UV-1 0.100
UV-2 0.060
UV-3 0.095
UV-4 0.013
UV-5 0.200
F-11 0.009
S-1 0.086
HBS-1 0.175
HBS-4 0.050
Gelatin 1.984

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
W-5 0.025
W-1 9.0 × 10 ⁻³
S-1 0.200
Gelatin 0.750

  Furthermore, in order to improve the preservability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coatability as appropriate for each layer, B-4 to B-6, F-1 to F-17 and Lead salts, platinum salts, iridium salts and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye The solid disperse dye ExF-2 of the twelfth layer was dispersed by the following method.
ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate
(31 mass% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
4.020 kg of water
Total 7.210kg
(Adjusted to pH = 7.2 with NaOH)

After the slurry having the above composition is roughly dispersed by stirring with a dissolver, it is dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a filling rate of zirconia beads having a diameter of 0.3 mm of 80%. Dispersion was performed until the absorbance ratio of the liquid reached 0.29 to obtain a solid fine particle dispersion. The average particle size of the dye fine particles was 0.29 μm.
Similarly, solid disperse dyes ExF-4 and ExF-9 were obtained. The average particle diameters of the fine dye particles were 0.28 μm and 0.49 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

Hereinafter, compounds used for preparing each layer are shown.

The color negative photosensitive material prepared as described above is referred to as Sample 101.
The compound of the present invention is added to the 11th layer, 7th layer and 12th layer of the sample 101 as shown in Table 2, and the amount of UV-1 to 5 of the 15th layer (first protective layer) is changed. Thus, samples 102 to 148 were prepared in the same manner as sample 101 except that the spectral sensitivity in the ultraviolet region was changed to have the spectral sensitivity distribution of the blue photosensitive layer as shown in Table 2 at a concentration of Dmin + 0.5. .

The above samples were evaluated for sensitivity, granularity, radiation resistance, and charge control ability test.
(Evaluation of sensitivity and graininess)
Samples 101 to 148 were exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge. Then, the following process was performed.
The sensitivity is shown as a relative value when the reciprocal of the exposure amount that gives the minimum density +0.2 as the magenta color image density of the sample 101 is 100.
Graininess was evaluated by determining the RMS granularity of a magenta color image at a fog + 0.2 density. The relative value when the sample 101 is 100 is shown.
In order to evaluate the substantial increase in sensitivity, when the RMS granularity changes with the increase in sensitivity, the amount of ExY-3 in the sixth, eleventh, and fourteenth layers is adjusted so that the RMS granularity matches. And compared.

(Evaluation of radiation resistance)
After irradiating the coated samples 101 to 148 with 0.2 R of γ rays (1.173, 1.333 MeV) of the radioisotope element ⁶⁰ Co, development processing is performed in the same manner as the light exposure described above, and the density is measured for magenta color development. Thus, the fog density value was determined. From this and the fog density of the sample used in the previous exposure, the increase in fog due to radiation irradiation was determined, and the relative value of the fog increase of sample 101 was determined.

(Evaluation of charge adjustment test)
About each sample, it processed into 135 format, and the thing accommodated in the film cartridge was loaded in the camera, it wound up at high speed in the environment of temperature 15 degreeC humidity 15%, developed after the following process, and the fog was visually observed. .

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)
5:95 (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

  Table 2 shows the results of the sensitivity, granularity, radiation coverage, and charge adjustment ability characteristics of Samples 101 to 148. As is apparent from Table 2, the comparative example has a large radiation cover, but it can be seen that the present invention can provide a photosensitive material excellent in sensitivity and granularity without increasing the radiation cover.

<Example 2>
Samples 201 to 207 are the same as Sample 113 except that W-1 of the 16th layer (second protective layer) is changed to the compound shown in Table 3 with an equal mass with respect to Sample 113 of Example 1. Was made.
The above samples were evaluated for sensitivity, granularity, radiation resistance, charge adjustment ability test, and high-speed coating suitability test. The treatment was performed in the same manner as in Example 1.
Evaluation of sensitivity, granularity, radiation resistance, and charge adjustment ability test were performed in the same manner as in Example 1.

(Evaluation of high-speed application suitability test)
The particle size of B-1 of the 16th layer is 3 μm, applied at 1 m / sec by the slide bead coating method, and then dried immediately. The number of repellants generated on the coating film surface is visually counted, Indicated. The repelling frequency indicates the repelling number of each sample as a percentage with respect to the repelling number of the sample 201. When the repelling frequency is 100 or less, it is determined that the repelling effect is effective.

  Table 3 shows the results of the sensitivity, granularity, radiation covering, charge controllability characteristics, and high-speed coating suitability test for Samples 201 to 207. As is apparent from Table 3, it can be seen that by adding the surfactant of the present invention, a photosensitive material excellent in high-speed coating suitability in addition to the effects of Example 1 can be obtained.

<Example 3>
A sample similar to the sample 101 of Example 1 is designated as 301.
Samples 302 to 348 were prepared in the same manner as Samples 102 to 148 except that the compound of the present invention added to the 11th layer in Table 2 of Example 1 was added to the 6th layer as shown in Table 2.

  As a result of evaluating the following sensitivity, granularity, radiation resistance, and charge control ability test for the above samples, good results were obtained as in Example 1. The processing was performed in the same manner as in Example 1.

(Evaluation of sensitivity and graininess)
Samples 301 to 348 were exposed for 1/100 second through gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge. Then, the following process was performed.
Sensitivity is shown as a relative value when the reciprocal of the exposure amount that gives the minimum density +0.2 for the cyan color image density is 100.
Graininess was evaluated by determining the RMS granularity of a cyan image at a density of fog + 0.2. The relative value when the sample 101 is 100 is shown.
In order to evaluate the substantial increase in sensitivity, when the RMS granularity changes with the increase in sensitivity, the amount of ExY-3 in the sixth, eleventh, and fourteenth layers is adjusted so that the RMS granularity matches. And compared.

(Evaluation of radiation resistance)
After irradiating the coated samples 301 to 313 with 0.2 R of γ rays (1.173, 1.333 MeV) of radioisotope element ⁶⁰ Co, development processing is performed in the same manner as the above-described light exposure, and the density is measured for cyan color development. Thus, the fog density value was determined. From this and the fog density of the sample used in the previous exposure, the increase in fog due to the irradiation of radiation was determined, and the relative value of the fog increase of sample 301 was determined.

(Evaluation of charge adjustment test)
About each sample, it processed into 135 format, and the thing accommodated in the film cartridge was loaded in the camera, it wound up at high speed in the environment of temperature 15 degreeC humidity 15%, developed after the following process, and the fog was visually observed. .

<Example 4>
The same as Samples 201 to 207 except that W-1 of the 16th layer (second protective layer) is changed to a compound as shown in Table 3 of Example 2 with an equal mass with respect to Sample 313 of Example 3. Thus, Samples 401 to 407 were produced.
The above samples were evaluated for sensitivity, granularity, radiation resistance, charge adjustment ability test, and high-speed coating suitability test. The treatment was performed in the same manner as in Example 1.
As a result of evaluation of sensitivity, granularity evaluation, radiation resistance evaluation, charge adjustment ability test, and high-speed coating suitability test, good results were obtained as in Example 2.

<Example 5>
A sample similar to the sample 101 of Example 1 is designated as 501.
Samples 502 to 548 were prepared in the same manner as Samples 102 to 148 except that the compound of the present invention added to the 11th layer in Table 2 of Example 1 was added to the 6th layer as shown in Table 2.
As a result of evaluating the following sensitivity, granularity, radiation resistance, and charge adjustment ability test for the above samples, good results were obtained as in Example 1. The processing was performed in the same manner as in Example 1.

(Evaluation of sensitivity and graininess)
Samples 501 to 548 were exposed for 1/100 second through a gelatin filter SC-39 manufactured by Fuji Film Co., Ltd. and a continuous wedge. Then, the following process was performed.
The sensitivity is shown as a relative value when the reciprocal of the exposure amount at which the yellow color image density of the sample 101 gives the minimum density +0.2 is 100.
Graininess was evaluated by determining the RMS granularity of a yellow color image at a density of fog + 0.2. The relative value when the sample 101 is 100 is shown.
In order to evaluate the substantial increase in sensitivity, when the RMS granularity changes with the increase in sensitivity, the amount of ExY-3 in the sixth, eleventh, and fourteenth layers is adjusted so that the RMS granularity matches. And compared.

(Evaluation of radiation resistance)
After irradiating the coated samples 501 to 513 with 0.2 R of γ rays (1.173, 1.333 MeV) of the radioisotope element ⁶⁰ Co, development processing is performed in the same manner as the light exposure described above, and the density is measured for yellow color development. Thus, the fog density value was determined. From this and the fog density of the sample used in the previous exposure, an increase in fog due to irradiation of the radiation was determined, and a relative value to the increase in fog of the sample 501 was determined.

(Evaluation of charge adjustment test)
About each sample, it processed into 135 format, and the thing accommodated in the film cartridge was loaded in the camera, it wound up at high speed in the environment of temperature 15 degreeC humidity 15%, developed after the following process, and the fog was visually observed. .

<Example 6>
The same as Samples 201 to 207 except that W-1 of the 16th layer (second protective layer) is changed to a compound as shown in Table 3 of Example 2 with an equal mass with respect to Sample 513 of Example 5 Thus, Samples 601 to 607 were produced.

  The above samples were evaluated for sensitivity, granularity, radiation resistance, charge adjustment ability test, and high-speed coating suitability test. The treatment was performed in the same manner as in Example 1.

  As a result of evaluation of sensitivity, granularity evaluation, radiation resistance evaluation, charge adjustment ability test, and high-speed coating suitability test, good results were obtained as in Example 2.

<Example 7>
A support was prepared by the following method.
1) First layer and undercoat layer A polyethylene naphthalate support having a thickness of 90 μm has a treatment atmosphere pressure of 0.2 Torr, a H ₂ O partial pressure of 75% in an atmospheric gas, a discharge frequency of 30 kHz, and an output of 2500 W on each side. The glow discharge treatment was performed at a treatment strength of 0.5 kV · A · min / m ² . On this support, a coating solution having the following composition was applied as a first layer in a coating amount of 5 mL / m ² using the bar coating method disclosed in Japanese Examined Patent Publication No. 58-4589.
Conductive fine particle dispersion 50 parts by mass (Aqueous dispersion with SnO ₂ / Sb ₂ O ₅ particle concentration of 10%.
(Secondary agglomerates with a primary particle size of 0.005 μm and an average particle size of 0.05 μm)
Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene 0.1 part by weight
Sorbitan monolaurate

Further, after coating the first layer, it is wound around a stainless steel core having a diameter of 20 cm, and heat-treated at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours and subjected to an annealing treatment, and then supported. A coating solution having the following composition was applied as an undercoat layer for emulsion on the side opposite to the first layer side with a bar coating method at a coating amount of 10 mL / m ² .
Gelatin 1.01 parts by mass Salicylic acid 0.30 parts by mass Resorcin 0.40 parts by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether
0.11 parts by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n-propanol 10.08 parts by mass

  Furthermore, the second and third layers described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is applied on the opposite side to form a transparent layer with a silver halide emulsion layer. A magnetic recording medium was produced.

2) Second layer (transparent magnetic recording layer)
(I) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A / m, σ s: 77.1 Am ² / kg, σr: 37.4 Am ² / kg) 1100 parts by mass, 220 parts by mass of water, and silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] 165 parts by mass Part was added and kneaded well with an open kneader for 3 hours. This coarsely dispersed viscous liquid was dried at 70 ° C. for one day to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Furthermore, it knead | mixed again with the following prescription for 4 hours with the open kneader.
Surface-treated magnetic particles 855 g
Diacetylcellulose 25.3 g
Methyl ethyl ketone 136.3 g
Cyclohexanone 136.3 g

Furthermore, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2000 rpm for 4 hours. The media used were 1 mmφ glass beads.
45 g of the above kneaded liquid
Diacetylcellulose 23.7 g
Methyl ethyl ketone 127.7 g
Cyclohexanone 127.7 g
Furthermore, the magnetic substance containing intermediate liquid was produced with the following prescription.

(Ii) Preparation of magnetic substance-containing intermediate liquid 674 g of the above magnetic substance fine dispersion
Diacetylcellulose solution 24280 g
(Solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Cyclohexanone 46 g
After mixing these, it stirred with the disperser and the "magnetic substance containing intermediate liquid" was produced.

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.
(A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumikorandom AA-1.5 152 g
Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicon Co., Ltd.) 0.48 g
Diacetylcellulose solution 227.52 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Using the above formulation, fine dispersion was performed at 800 rpm for 4 hours using a ceramic-coated sand mill (1/4 G sand mill). As the media, 1 mmφ zirconia beads were used.

(B) Colloidal silica particle dispersion (fine particles)
“MEK-ST” manufactured by Nissan Chemical Co., Ltd. was used.
This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and the solid content is 30%.

(Iii) Preparation of second layer coating solution 19053 g of the above magnetic substance-containing intermediate solution
Diacetylcellulose solution 264 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Colloidal silica dispersion “MEK-ST” [dispersion b] 128 g
(Solid content 30%)
AA-1.5 dispersion [dispersion a] 12 g
Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g
(Solid content 20%, diluent solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Methyl ethyl ketone 170 g
Cyclohexanone 170 g

The coating solution obtained by mixing and stirring the above was coated with a wire bar so that the coating amount was 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the magnetic layer after drying was 1.0 μm.

3) Third layer (layer containing higher fatty acid ester slip agent)
(I) Preparation of Dispersion Stock Solution of Sliding Agent The following solution A was heated and dissolved at 100 ° C., added to the solution A, and then dispersed with a high-pressure homogenizer to prepare a dispersion stock solution of slip agent.
Liquid A The following compound 399 parts by mass C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H ₁₀₁
The following compound 171 parts by mass nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
Cyclohexanone 830 parts by mass Liquid I Cyclohexanone 8600 parts by mass

(Ii) Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicon Co.)
Compound _{1-1: (CH 3 O) 3} Si- (CH 2) 3 -NH 2)
5.53 parts by mass W-5 2.93 parts by mass Seahosta KEP50 88.00 parts by mass (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.)

  After stirring for 10 minutes according to the above formulation, the following is added.

252.93 parts by mass of diacetone alcohol While cooling and stirring the above solution, the ultrasonic homogenizer “SONIFIER450”
(BRANSON Co., Ltd.) ”was used for 3 hours to complete spherical inorganic particle dispersion c1.

(Iii) Preparation of spherical organic polymer particle dispersion Liquid spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

60 parts by mass of XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm)
120 parts by mass of methyl ethyl ketone 120 parts by mass of cyclohexanone (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
While cooling with ice and stirring, the mixture was dispersed for 2 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON)” to complete a spherical organic polymer particle dispersion c2.

(Iv) Preparation of third layer coating solution The third layer coating solution was prepared by adding the following to 542 g of the slip agent dispersion stock solution.
Diacetone alcohol 5950 g
Cyclohexanone 176 g
Ethyl acetate 1700 g
Seahosta KEP50 dispersion [c1] 53.1 g
300 g of the above spherical organic polymer particle dispersion [c2]
FC431 2.65 g
(3M Co., Ltd., solid content 50%, solvent: ethyl acetate)
BYK310 5.3 g
(BYK Kemi Japan Co., Ltd., solid content 25%)

The third layer coating solution was applied onto the second layer at a coating amount of 10.35 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of photosensitive layer Next, the layers of the compositions of Samples 101 to 148 were applied in layers on the opposite side of the obtained back layer to prepare a color negative film.
Each sample was processed into an advanced photo system format, and the one stored in a dedicated cartridge was loaded into a camera. The same tests as in Examples 1 to 6 were conducted and evaluated. Good results were obtained as in Example 6.

Claims (2)

Each of the support has at least one blue-sensitive layer, green-sensitive layer, red-sensitive layer, and non-photosensitive layer, and at least one layer contains the following compound (A) or compound (B), A silver halide color photographic material, wherein the spectral sensitivity distribution S _B (λ) of the blue-sensitive layer satisfies the relationship of the following formula (1).
Compound (A): a compound that is a heterocyclic compound having one or two heteroatoms, and by adding this compound, the sensitivity of the silver halide photographic material is substantially increased as compared with the case where it is not added (B): a heterocyclic compound having 3 or more heteroatoms, which is a compound which, when added, substantially increases the sensitivity of the silver halide photographic light-sensitive material as compared with the case where it is not added, and oxidative development Compound formula (1) which does not react with main drug: S _B (370 nm) / S _B (420 nm) <0.7 The silver halide color photographic light-sensitive material according to claim 1, comprising at least one fluorine-based surfactant represented by the following general formula (X) or general formula (Y).
Formula (X)

In the general formula (X), R ^B3 , R ^B4 and R ^B5 each independently represent a hydrogen atom or a substituent. A and B each independently represent a fluorine atom or a hydrogen atom. n ^B3 and n ^B4 each independently represents an integer of 4 to 8. L ^B1 and L ^B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. m ^B represents 0 or 1. M represents a cation.
General formula (Y)

In the general formula (Y), R ^C1 represents a substituted or unsubstituted alkyl group (wherein the substituent does not include a fluorine atom), and R ^CF represents a perfluoroalkylene group. A represents a hydrogen atom or a fluorine atom, and L ^C1 represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining these. One of Y ^C1 and Y ^C2 represents a hydrogen atom, the other represents —L ^C2 —SO ₃ M, L ^C2 represents a single bond or a substituted or unsubstituted alkylene group, and M represents a cation.