JP2005084587A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for increasing the sensitivity of a silver halide photographic sensitive material without degrading image quality such as graininess. <P>SOLUTION: A silver halide photographic sensitive material is provided which contains a sensitizing dye and a compound having one or more aromatic hydrocarbon rings or aromatic heterocycles, wherein the compound interacts with the sensitizing dye by attraction in development and the interaction has sufficiently high force to increase the photographic sensitivity of the sensitive material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide photographic light-sensitive material having increased photographic sensitivity, particularly preferably a silver halide color photographic material, and a method for obtaining an image having increased photographic sensitivity.

  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 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. 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.

  A technique for increasing sensitivity without deteriorating graininess by incorporating a compound having at least three heteroatoms that do not react with an oxidized developing agent into a silver halide photographic material has been disclosed. (For example, refer to Patent Document 1).

  However, although the sensitivity is increased by the method described in this published patent, the effect is not sufficient, and it has been found that there are side effects due to the addition of the compound. When the compound coexists with the silver halide emulsion, an unfavorable interaction occurs, and an undesirable deterioration with time occurs when the coating solution is stored or when the photosensitive material is stored.

JP 2000-194085 A

  As a result of continuous studies to obtain the above-mentioned greater effect and to solve the problems, the present inventors have obtained one or more aromatic hydrocarbon rings or aromatic heterocycles that interact with the sensitizing dye. The present inventors have found a method for increasing sensitivity preferably by using a compound having the same. Although the detailed mechanism is unknown, it has been found that compounds that interact with sensitizing dyes are advantageous for this purpose.

  Since the present invention relates to a method for improving the sensitivity / granularity of a light-sensitive material using a compound that interacts with a sensitizing dye, the sensitivity is increased by using a compound that does not substantially interact with the sensitizing dye. This is different from the configuration of Japanese Patent Laid-Open No. 2000-194085 that describes the photosensitive material.

  An object of the present invention is to provide a method for increasing the sensitivity without deteriorating the image quality such as the graininess of a silver halide photographic light-sensitive material (preferably a silver halide color photographic light-sensitive material).

  The present inventors have found that the above problem can be solved by using a compound having one or more aromatic hydrocarbon rings or aromatic heterocycles that interact with the following sensitizing dyes. The action mechanism of the compound of the present invention is considered to be effective by eliminating sensitivity loss during development. From the analysis results, the compound of the present invention interacts with the sensitizing dye on the emulsion surface during development, thereby weakening the adsorption of the sensitizing dye and activating the normally undeveloped latent image to increase the development starting point. Estimated. The sensitizing dye is present on the surface of the emulsion grain at the time of photographing and is essential for increasing the optical sensitivity, but it may inhibit the oxidation developing agent from reacting with the latent image during development. When the compound of the present invention is emulsified and dispersed, the compound of the present invention is present in the oil droplet at the time of photographing, dissociates under the high pH condition of the developer and elutes from the oil droplet and acts on the sensitizing dye on the emulsion grain surface. To do. In order to exhibit this characteristic more effectively, it has been found that it is effective to design the pKa to be a value near or lower than the developer pH. By having such characteristics, it exhibits a greater effect than the exemplary compounds described in JP-A No. 2000-194085, and is a sensitizing dye that is not preferred during the production of a photosensitive material (photosensitive material) or during storage of the photosensitive material. Realized to reduce the interaction.

  As a result of further studies, it was found that the use of the above compounds not only activates the latent image on the emulsion surface during development and enhances the reactivity with the oxidized developing agent, but also makes it easier to undergo latent image bleaching due to oxidation. . For this reason, it has been found that if the interaction of the compound of the present invention with the sensitizing dye is made too high, latent image bleaching occurs simultaneously and the preferable effect of increasing the development starting point may be reduced.

  That is, the present invention provides the following method.

(1) A silver halide photographic light-sensitive material containing a sensitizing dye and a compound having at least one aromatic hydrocarbon ring or aromatic heterocyclic ring, wherein the compound interacts with the sensitizing dye by attraction during development. A silver halide photographic light-sensitive material that acts and the interaction is large enough to increase the photographic sensitivity of the light-sensitive material.
(2) The silver halide photographic light-sensitive material according to (1), wherein the silver halide photographic light-sensitive material according to (1) is a silver halide color photographic light-sensitive material.
(3) The compound according to (1) or (2) is a compound having three or more aromatic hydrocarbon rings or aromatic heterocycles. The silver halide photographic light-sensitive material described. More preferably, the compound is a compound having three or more aromatic hydrocarbon rings.
(4) A silver halide photographic light-sensitive material containing a compound represented by the following general formula (H), wherein the photographic sensitivity is increased as compared with the same light-sensitive material except that the compound is not contained. A silver halide photographic light-sensitive material characterized by
Formula _{(H) A 1 - (X} 1) n 1 -B 1 - (X 2) n 2 -A 2 Mdmd
In the formula, A ₁ and A ₂ represent an aryl group or an aromatic heterocyclic group, B ₁ represents an atomic group having π electrons, and X ₁ and X ₂ represent a linking group. n ₁ and n _{2 each} represents 0 or 1; Md represents a charge balanced counter ion, and md represents a number of 0 or more necessary to neutralize the charge of the molecule.
(5) The compound described in (1) or (2), wherein the compound described in (1) or (2) is a compound represented by the general formula (H) described in (4) Silver halide photographic light-sensitive material.
(6) The increase in the film pAg (ΔpAg _F ) of the silver halide (preferably color) photographic material due to the addition of the above compound is 0 or more and 0.3 or less, (1) to (5) The silver halide photographic light-sensitive material according to any one of the above.
(7) The silver halide photographic light-sensitive material as described in any one of (1) to (6) above, wherein the compound has a pKa of from 5.5 to 8.4.
(8) The silver halide (preferably color) photographic light-sensitive material according to any one of (1) to (7), wherein the compound is contained in a red-sensitive silver halide emulsion layer.
(9) The silver halide (preferably color) photographic light-sensitive material according to any one of (1) to (8), wherein the compound is contained in a green sensitive silver halide emulsion layer.
(10) The silver halide (preferably color) photographic light-sensitive material according to any one of (1) to (9), wherein the compound is contained in a blue-sensitive silver halide emulsion layer.
(11) The halogenation according to any one of (1) to (10), wherein the layer containing tabular grains having an average aspect ratio of 8 or more contains at least one compound among the compounds. Silver photographic material.
(12) A method for increasing the photographic sensitivity of a silver halide photographic light-sensitive material by using a compound having at least one aromatic hydrocarbon ring or aromatic heterocycle having the property of interacting with a sensitizing dye during development (the compound). .
(13) A method for increasing the photographic sensitivity of a silver halide photographic light-sensitive material with the compound represented by the general formula (H) described in (4).

  According to the present invention, a highly sensitive silver halide photographic light-sensitive material can be obtained.

Hereinafter, the present invention will be described in detail.
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. In addition, the substituent that can be used in the compound in the present invention may be any substituent.

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, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and the like 1-methyl-2-pyridinio and 1-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, Propoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), 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), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy A group (preferably a substitution of 2 to 30 carbon atoms 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, A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom) To 30 substituted or unsubstituted carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn -Octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy) An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ), An amino group (preferably 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 by a heterocycle, For example, trimethylammonio, triethylammonio, diphenylmethylammonio), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, Unsubstituted arylcarbonylamino group such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably C1-C30 substituted or unsubstituted aminocarbonylamino, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably carbon A substituted or unsubstituted alkoxycarbonylamino group of 2 to 30, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino A group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino) Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a group having 1 to 30 carbon atoms). Or an unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio) A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably having a carbon number) 0 to 30 substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N- Benzoylsulfamoyl, N- (N′-F Nylcarbamoyl) 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) , For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, from 7 carbon atoms 30 substituted or unsubstituted arylcarbonyl groups, a heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, Benzoyl, pn-octyloxyphenylcarbonyl, 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 methoxycarbo , Ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethyl) Carbamoyl, 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, 3 to 30 carbon atoms) Substituted or unsubstituted heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide groups (preferably N-succinimide, N-phthalimide) ), Phosphino group (preferably carbon number) To 30 substituted or unsubstituted phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl , Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyl Oxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), phosphor Group, silyl group (preferably having 3 carbon atoms To 30 substituted or unsubstituted silyl groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino groups (preferably substituted or unsubstituted hydrazino groups having 0 to 30 carbon atoms such as trimethylhydrazino ), A ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, 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, phenothiazine ring or a phenazine ring, and the like.) Can 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, an alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), or an arylsulfonyl An aminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

Hereinafter, the compound having at least one aromatic hydrocarbon ring or aromatic heterocyclic ring having the property of interacting with a sensitizing dye sufficient to increase the photographic sensitivity of the present invention will be described in detail.
The compounds used in the present invention are characterized by having the property of interacting with a sensitizing dye sufficient to increase photographic sensitivity.

  Examples of the interaction include van der Waals force (more precisely, an orientation force acting between a permanent dipole and a permanent dipole, an induced force acting between a permanent dipole and an induced dipole, It can be expressed in terms of the dispersion force acting between the dipole and the induced dipole.), Charge transfer force (CT), Coulomb force (electrostatic force), hydrophobic bond force, hydrogen bond force, coordination bond force, etc. Only one of these binding forces can be used, or a plurality of arbitrary binding forces can be used in combination. Preferably, van der Waals force, charge transfer force, Coulomb force, hydrophobic bond force, hydrogen bond force, more preferably van der Waals force, hydrophobic bond force, hydrogen bond force, particularly preferably Van der Waals power.

  The degree of interaction with the sensitizing dye may be any strength as long as it is strong enough to increase photographic sensitivity, but a stronger interaction is preferred. The term “interacting” means that the compound of the present invention and the sensitizing dye interact with each other by attractive force, and the attractive energy (ΔG) is preferably 15 kJ / mol or more, more preferably 20 kJ / mol or more. Particularly preferred is the case of 40 kJ / mol or more. Although there is no upper limit in particular, it is preferably 5000 kJ / mol or less, more preferably 1000 kJ / mol or less.

  The attraction energy of the compound of the present invention and the sensitizing dye is determined by the association constant K of the equilibrium of formation of the aggregate represented by the formula (1) between the compound (DA) of the present invention and the sensitizing dye (dye) below. Can be estimated. Formula (1) assumes that a 1: 1 aggregate (DA · dye) is formed between the compound (DA) of the present invention and the sensitizing dye (dye). It can be expressed as When forming aggregates at other ratios, the calculation formula changes, but there is no essential difference, so in the present invention, all aggregates are treated as 1: 1 aggregates. The association constant can be determined according to the principle of a normal equilibrium constant described in many books (for example, Koichiro Kayama, “Chemical Thermodynamics”, Agne Technical Center (2002)). Here, a measurement example will be described in detail below.

At this time, the concentration of the compound of the present invention that does not form an aggregate is [DA], the concentration of the sensitizing dye that does not form an aggregate is [dye], and the concentration of the aggregate is [DA · dye]. The association constant K is expressed by equation (2).

When the total concentration of the compound of the present invention in the solution is [DA] ₀ and the total concentration of the sensitizing dye in the solution is [dye] ₀ , the formula (2) is

When [DA] ₀ >> [DA ・ dye]

Can be approximated. From this, the aggregate concentration [DA · dye] is expressed by the formula (3).

Since the solution absorption spectrum of the association between the compound of the present invention and the sensitizing dye (DAdye) changes compared to the solution absorption spectrum of the sensitizing dye alone without the addition of the compound of the present invention, the absorption spectrum changes. A large specific wavelength can be selected as the measurement wavelength, and the change in absorbance at that wavelength can be measured.
For example, assuming that the absorbance when the mixed solution of the compound of the present invention and the sensitizing dye at this measurement wavelength is measured in a cell having an optical path length of 1 cm is A, by using formula (3), A can be expressed by formula (4). It is represented by

Where εs represents the molar extinction coefficient at the measurement wavelength of the sensitizing dye alone, and εc represents the molar extinction coefficient at the measurement wavelength of the aggregate.
On the other hand, the absorbance A _{0 at} the measurement wavelength of the sensitizing dye single solution is represented by the formula (5).

  From equations (4)-(5)

Therefore,

Thus, it is understood that a straight line can be obtained by plotting the reciprocal of the change in absorbance at the measurement wavelength against the reciprocal of the total concentration in the solution of the compound of the present invention. If the slope of this straight line is a and the intercept is b,

Thus, the association constant K can be obtained from the intercept / slope of the straight line.

  An example of specific measurement conditions for the association constant is described below. The solvent used for the measurement was a solvent prepared by mixing 38.2 g of potassium carbonate and 4.2 g of sodium bicarbonate in 1 L of water (fine adjustment with sulfuric acid to pH = 10.05) and dimethylformamide in a ratio of 8.5 to 1.5. Was used. A sample was prepared by dissolving the sensitizing dye 1 having the following structure and the compound of the present invention in this solvent so as to have the concentrations shown in the table below.

The absorption spectrum of each sample was measured at 25 ° C., and the reciprocal of the value obtained by subtracting the absorbance at 580 nm of sample 1 from the absorbance at 580 nm of samples 2 to 6 was determined. The association constant can be determined by plotting the determined value against the reciprocal of the total concentration of the compound of the present invention in the solution and dividing the intercept of the obtained correlation line by the slope.
Under these conditions, the compound (A-2) of the present invention described later had log K = 4.6, and (A-3) had log K = 4.3.
The value of log K of the compound of the present invention is preferably in the range of 1 to 10, more preferably 3 to 9, particularly preferably 4 to 8.

  In order to cause interaction with a sensitizing dye, a compound containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring in the molecule (hereinafter, this compound may be simply referred to as “the compound of the present invention”). ) Are preferred, more preferred are compounds containing 3 or more aromatic hydrocarbon rings and aromatic heterocycles in total, and particularly preferred are compounds containing 5 or more. There is no particular upper limit on the total number of aromatic hydrocarbon rings or aromatic heterocycles, but it is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less. Here, the condensed ring system calculates each ring, and for example, the naphthalene ring is counted as two.

Examples of the skeleton of the compound of the present invention preferably used include those of the following document [A].
Reference [A]:
Bistriazinyl-substituted stilbene compounds (the skeletons of these compounds are described in JP-A-6-329936, JP-A-7-140625, JP-A-10-104809 or JP-A-2001-281823, “Dyeing Note” 19th edition (color Dyeing) P.165 to P.168)), bisaryl-substituted triazine compounds (the skeletons of these compounds are described in US Pat. No. 6,153,364, etc.), Bistriazinyl-substituted arylene compounds (the skeletons of these compounds are described in JP-A No. 2002-139822), bisaryl-substituted arylene compounds (for the skeletons of these compounds, Japanese Patent Application No. 2002-352759, Japanese Patent Application No. No. 2002-355512, Japanese Patent Application No. 2002-60245 Bispyrimidyl-substituted stilbene compounds (the skeletons of these compounds are described in JP-A-6-161017, US Pat. No. 4,596,767, etc.)
Among the above, preferably a bistriazinyl-substituted stilbene compound, a bisaryl-substituted triazine compound, a bisaryl-substituted arylene compound, and a bispyrimidyl-substituted stilbene compound, more preferably a bisaryl-substituted triazine compound and a bisaryl-substituted arylene compound, particularly preferably Bisaryl substituted arylene compound.

As the compound of the present invention, a compound represented by the general formula (H) is particularly preferably used.
The compound represented by formula (H) will be described in detail.
A ₁ and A ₂ represent an aryl group or an aromatic heterocyclic group, and the aryl group is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples include the aforementioned W. Specifically, phenyl, 3-carboxyphenyl, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 4-sulfophenyl group, 1-naphthyl, 2-naphthyl, 5-sulfo-2-naphthyl, 5-carboxy-2-naphthyl, 6-carboxy-1-naphthyl, 1-anthryl, 5-phenanthryl, etc.), preferably an aromatic heterocyclic group having 2 carbon atoms. To 20, more preferably 2 to 10 carbon atoms, particularly preferably a substituted or unsubstituted 5- or 6-membered heterocyclic group (substituent) having 2 to 8 carbon atoms. Examples include W described above, and specific examples include 2-furyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, and the like. Preferably, it is a substituted or unsubstituted naphthyl group.

B ₁ represents an atomic group having π electrons, and preferably a carbonyl, double bond (eg, carbon-carbon double bond, carbon-nitrogen double bond, etc.), triple bond (eg, carbon-carbon A triple bond of carbon, a triple bond of nitrogen and the like), a divalent aromatic hydrocarbon ring, or an aromatic heterocycle. Preferably, it is an aromatic ring, a hydrocarbon ring, or a heterocyclic ring. For example, the benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring described in the above W, Pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine 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, thianthrene ring, chromene ring, xanthene ring, phenoxathiin , Phenothiazine ring, and phenazine ring, preferably a benzene ring, a pyridine ring, a pyrimidine ring, and a triazine ring having 2 to 20 carbon atoms, more preferably a benzene ring and a pyrimidine ring. A ring, a triazine ring. These may be substituted with a substituent (for example, W described above). A benzene ring or a triazine ring is preferable, and a benzene ring is more preferable.
B ₁ is preferably further substituted with-(X ₃ ) n ₃ -A ₃ . Here, X ₃ has the same meaning as X ₁ or X _2, and the same can be mentioned, and the same is preferable. A ₃ has the same meaning as A ₁ or A _2, and the same can be mentioned and the same is preferable. n ₃ represents 0 or 1, and is preferably 1.

X ₁ and X ₂ represent a linking group, and examples thereof include a linking group described in La described later. Preferably, CHR ₁ , CR ₁ = CR ₁ , NR ₁ , O, S, C═O, CONR ₁ , SO ₂ NR ₁ , CO ₂ can be mentioned (R ₁ represents a hydrogen atom or a substituent. as the base, for example, there may be mentioned W described above, preferably an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group as .R _1, particularly preferably a hydrogen atom, a methyl group, Ethyl group, i-propyl group and n-propyl group.), More preferably NR ₁ , O, S, C═O, CONR ₁ , SO ₂ NR ₁ , CO ₂ , particularly preferably NR ₁ , CONR ₁ .

n ₁ and n ₂ represent 0 or 1, but preferably both are 1. Md represents a charge-balanced counterion and is included in the formula to indicate the presence of a cation or anion when necessary to neutralize the ionic charge of the compound of general formula (H). . 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. An anion is preferable, a sodium ion and a potassium ion are more preferable, and a sodium ion is particularly preferable. md represents a number of 0 or more necessary for neutralizing the charge of the molecule, preferably a number of 0 to 4, more preferably a number of 0 to 2.

As the substituent of the compound of the present invention, any substituent can be selected for obtaining desired photographic characteristics for a specific application used by those skilled in the art. 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 carbon atoms, 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.
Specifically, an alkyl group (carbon number 8 to 60. For example, t-octyl, 1-ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), an alkenyl group (carbon number 8 to 8). 60. For example, oleyl), cycloalkyl group (carbon number 8 to 60. For example, 1-indanyl, cyclododecyl), aryl group (carbon number 8 to 60. For example, t-butylphenyl, naphthyl), acylamino group (carbon Number 8 to 60. For example, octanoylamino, 2-hexyldecanamide, 2- (2 ′, 4′-di-t-amylphenoxy) butanamide, nicotinamide), sulfonamide group (carbon number 8 to 60. For example, Octanesulfonamide, t-butylbenzenesulfonamide), ureido group (carbon number 8-60. , Decylaminocarbonylamino, di-n-octylaminocarbonylamino), urethane group (carbon number 8 to 60. For example, dodecyloxycarbonylamino, t-butylphenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), alkoxy group ( Carbon number 8 to 60. For example, n-octyloxy, hexadecyloxy), aryloxy group (carbon number 8 to 60. For example, t-butylphenoxy, 2,4-di-t-amylphenoxy, 4-t-octyl. Phenoxy, naphthoxy), alkylthio group (carbon number 8 to 60. For example, hexadecylthio), arylthio group (carbon number 8 to 60. For example, 4-todecyloxyphenylthio), acyl group (carbon number 8 to 60. For example, Dodecanoyl), sulfonyl group (carbon number 8 to 60. For example, t- Butylbenzenesulfonyl), carbamoyl group (8 to 60 carbon atoms, for example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (8 to 60 carbon atoms, for example, N, N-dioctylsulfamoyl), alkylamino group (carbon) Number 8 to 60. For example, octylamino, octadecylamino), arylamino group (carbon number 8 to 60. For example, t-butylphenylamino, naphthylamino, N-octyl-N-phenylamino), heterocyclic group (carbon 8 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. The number of members is 3 to 8, more preferably 5 to 6. For example, the above-described group represented by W), acyloxy group (charcoal) 8 to 60. For example, myristoyloxy and benzoyloxy) are preferred.

Among them, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group Includes those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Sulfonyl group, cyano group, carbamoyl group, sulfamoyl group. 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, 8 or more and 60 or less are preferable, and 20 or more and 50 or less are more preferable.

  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, so that the compound of the present invention is dissociated and eluted from the oil only during development.
The pKa of the compound of the present invention is preferably 5.5 or more, more preferably 5.5 or more and 10.0 or less, particularly preferably 5.5 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, and any chemistry related to these and any known in the photographic field. 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, and therefore, it can be preferably used.

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

  In order to impart the above 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), 59-105640, 59-105641 and 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, 61-196240 (US Pat. No. 4,702,999), 61-185743, 61-124941 (US Pat. No. 4,639,408), and quinone by intramolecular electron transfer described in JP-A-2-280140. Blocking group utilizing the formation of a compound similar to methide or quinone methide, U.S. Pat. Nos. 4,358,525, 4,330,617, JP-A 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 JP 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 (US Pat. No. 4,690,885), 61-95347 (US Pat. No. 4,892,811), JP-A Nos. 64-7035 and 4-42650 (US Pat. No. 5,066,573), JP-A No. 1-245255, 2-207249, 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, Block groups utilizing β-elimination reactions described in 59-93442, 61-32839, 62-163051, and JP-B-5-37299, etc., described in JP-A-61-188540 Blocking groups utilizing nucleophilic substitution reactions of diarylmethanes, blocking groups utilizing the Rosen rearrangement described in JP-A-62-187850, JP-A-62-80646, JP-A-62-144163 and Blocking group utilizing reaction of N-acyl thiazolidine-2-thione with amines described in 62-147457, JP-A-2-296240 (US Pat. No. 5,019,492) 4-177243, 4-177244, 4-177245, 4-177246, 4-177247, 4-177247, 4-177248, 4-177249, 4-177948, It has two electrophilic groups described in 4-184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419, JP-A-5-45816, etc. Mention may be made of blocking groups that react with dinucleophiles, 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 polymer compound containing a partial structure of the compound of the present invention.
(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-56-12639, JP-A-55-155350, JP-A-55-155351, JP-A-63-27838, JP-A-63-197943, Europe. As disclosed in Japanese Patent No. 15,601 and the like, solid dispersions can be produced in the same manner as the dyes described therein.
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 in which the dye is fixed are disclosed in US Pat. Nos. 2,548,564, 4,124,386, and 3,625,694, and can be produced in the same manner as the dyes described therein.
(7) A method of immobilizing the compound of the present invention by adsorbing it to a metal salt such as silver halide. Examples of fixing dyes are disclosed in U.S. Pat. Nos. 2,719,088, 2,496,841, 2,496,843, and JP-A-60-45237. It can be produced in the same manner as the above dyes.
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 dimercapto-substituted nitrogen-containing telocyclic 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.

In addition, it is preferable not to contain the group represented by -N = N- and -SH in the molecule | numerator of the compound represented by general formula (H).
In addition, the sulfo group or the carboxy group may be protected with a group that decomposes by the attack of a nucleophile such as a hydroxide ion such as an ester group. The nucleophile has been described above.
Further, when the sulfo group is substituted, the diffusibility is high, so that the fixability during storage is inferior, and it is not preferable because it is eluted at the time of development processing. The case where it is not substituted is preferable.
Preferable examples of the compound represented by the general formula (H) are combinations of the above individual preferable ones (particularly, combinations of the individual most preferable ones).

  Next, among the compounds 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.

  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.

  The compound of the present invention can be synthesized on the basis of the methods described in the literatures and patents mentioned in the above-mentioned document [A] and the International Publication WO97 / 19916 pamphlet.

  It can be particularly preferably used when the compound of the present invention is contained in a silver halide photographic material. In such a case, in particular, a high sensitivity enhancement effect can be obtained.

In addition, the compound of the present invention can be used in combination with one or a plurality of arbitrary methods having a high sensitivity effect and compounds having a high sensitivity effect. Also in this case, the method used and the number and types of the compounds to be contained can be arbitrarily selected.
For example, the compound of the present invention may be used in combination with a compound having at least three heteroatoms described in JP-A Nos. 2000-194085 and 2003-156823.

  In the present invention, an image forming method for increasing the photographic sensitivity of a silver halide photographic light-sensitive material with a compound having at least one aromatic hydrocarbon ring or aromatic heterocycle having a property of interacting with a sensitizing dye. Can also be used.

In the present invention, it is sufficient that the compound of the present invention can be allowed to act on a silver halide photographic light-sensitive material (preferably a silver halide color photographic light-sensitive material). It is preferably contained in the photosensitive material.
When the silver halide photographic light-sensitive material contains the compound of the present invention, it may be used for either the silver halide light-sensitive layer or the non-light-sensitive 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 it in an organic solvent such as water or methanol, or a mixed solvent), and a method of adding it at the time of preparing a silver halide emulsion. 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. Furthermore, a dispersion method using an organic solvent-soluble polymer is described in International Publication No. 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 organic solvent is preferably used in an amount of 0 to 10 times, preferably 0 to 4 times the mass ratio of the residual color reducing agent compound used in 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 composition for coating 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, noodle washing or ultrafiltration.
The average particle size of the lipophilic fine particle dispersion (emulsified dispersion) thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.00. It is 08-0.20 μm. 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 ball mill, colloid mill, vibration ball mill, sand mill, jet mill, roller mill or ultrasonic wave, 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).

  As described in the Background section, photographic sensitivity is generally determined by the size of 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.

  “Increasing the photographic sensitivity” described in the claims of the present invention is not a method for increasing the sensitivity accompanied by the deterioration of graininess commensurate with the increase in sensitivity. The method for increasing the sensitivity of the present invention is a method for increasing the sensitivity without causing deterioration in graininess, or a method for increasing the sensitivity in which the increase in sensitivity is large compared to the deterioration in graininess. When the increase in sensitivity and the deterioration of graininess occur at the same time, it is necessary to match the graininess using the “adjusting means” and compare the sensitivities, and to substantially increase the sensitivity.

  A substantial increase in sensitivity is defined as a sensitivity difference of 0.03 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 +0.2. .

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

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

The increase in membrane pAg (ΔpAg _F ) due to the addition of the compound of the present invention is determined by the following method.
The increase in film pAg due to the addition of the compound of the present invention is determined by the difference in film pAg value from the case where the following evaluation light-sensitive material (A) is prepared and the compound of the present invention is not added. The membrane pAg value was determined by immersing a sensitive material having a size of 8 cm × 12 cm in 100 mL of the following buffer adjusted to pH 10 for 5 minutes, and measuring the pAg of the buffer using a silver electrode and a comparative electrode (sweet koji electrode). can get.
<Buffer preparation method>
Boric acid 7.73g
Potassium chloride 49.0g
Potassium carbonate 17.3g
1N aqueous potassium hydroxide solution 62.5mL
Add water to 1000mL

  The increase in membrane pAg due to the addition of the compound of the present invention is preferably from 0 to 0.3, more preferably from 0 to 0.25.

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 light-sensitive material to which the method of the present invention can be applied is not particularly limited, but preferably at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and non-light-sensitive layer are provided on the support. This is the case. As a typical example, a blue-sensitive, green-sensitive, and red-sensitive photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity are provided on a support. A silver halide photographic material having at least one non-photosensitive layer. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this 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 photosensitive layer are sequentially exposed to a support, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the degree is low. In addition, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer is provided on the side away from the support, and a high-sensitivity emulsion is provided on the side close to the support. Layers may be installed.

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 Japanese Patent Publication No. 55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-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. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive 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.

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 grain size of the silver halide may be fine grains having a diameter of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and 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), "Manufacture and coating of photographic emulsions" by Zerikman et al., 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, 4,439,520 and It can be easily prepared by the method described in GB 2,112,157.
It has also been found that the compounds for improving the sensitivity / granular ratio of the present invention exhibit a particularly great effect when used in the same layer as tabular grains having an average aspect ratio of 8 or more. 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, a core / shell type 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.

The light-sensitive material of the present invention preferably contains a “compound capable of emitting one electron or more electrons in a one-electron oxidant produced by one-electron oxidation”.
These compounds are preferably compounds selected from the following types 1 and 2.
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

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

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

In the formula, RED ₁ and RED ₂ represent a reducing group. R ₁ is a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form or hexahydro form of a 5-membered or 6-membered aromatic ring (including aromatic heterocycle) together with carbon atom (C) and RED ₁ Represent. R ₂ represents a hydrogen atom or a substituent. When a plurality of R ₂ are present in the same molecule, these may be the same or different. L ₁ represents a leaving group. ED represents an electron donating group. Z ₁ represents an atomic group that can form a 6-membered ring with a nitrogen atom and two carbon atoms of a benzene ring. X ₁ represents a substituent, and m 1 represents an integer of 0 to 3. Z ₂ represents —CR ₁₁ R ₁₂ —, —NR ₁₃ —, or —O—. R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a substituent. R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. X ₁₁ represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. L ₂ represents a carboxy group or a salt thereof, or a hydrogen atom. X ₂ represents a group which forms a 5-membered heterocycle with C═C. Y ₂ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation.

Next, the type 2 compound will be described.
As a compound that can be emitted by one-electron oxidant generated by one-electron oxidation with a type 2 compound and further undergoing a bond formation reaction, one or more electrons can be emitted from the general formula (10) The reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in Japanese Patent Application No. 2003-33446) may occur. And a compound represented by the general formula (11) (synonymous with the general formula (2) described in Japanese Patent Application No. 2003-33446). The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the above formula, X represents a reducing group that is one-electron oxidized. Y reacts with a one-electron oxidant formed by one-electron oxidation of X to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or benzo The reactive group containing the non-aromatic heterocyclic part of a condensed ring is represented. L ₂ represents a linking group for linking X and Y. R ₂ represents a hydrogen atom or a substituent. When a plurality of R ₂ are present in the same molecule, these may be the same or different. X ₂ represents a group which forms a 5-membered heterocycle with C═C. Y ₂ represents a group which forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation.

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

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

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

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. 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.

  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 (such as a trialkyl phosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group). 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.

  A preferred structure of the compound represented by types 1 and 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

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

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

  The compounds of type 1 and type 2 are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.

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

  Silver halide grains with fogged grain surface as described in US Pat. No. 4,082,553, silver halide grains with fogged grain interior as described in US Pat. No. 4,626,498, and JP-A-59-214852, colloidal silver as photosensitive silver halide emulsion It is preferably applied to the layer and / or the substantially non-photosensitive 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 the unexposed and exposed areas of the photosensitive material. 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).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.
The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized and does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.

The silver coating amount of the light-sensitive material of the present invention is preferably 8.0 g / m ² or less.
Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity increasing agent, right column, page 648 Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer to page 649, right column 4. Brightener 24 pages 647 pages right column 868 pages 5. 5. Light absorber, 25-26 pages, 649, right column, page 873 Filters, -page, left page, 650 Dyes, ultraviolet absorbers Binder page 26 page 651 left column page 873-874 Plasticizer, page 27, page 650, right column, page 876 Lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surface active agent 9. Static page 27 page 650 right column pages 876-877 inhibitor
Ten. Matting agent 878-879 pages

In the present invention, it is preferably used in combination with a technique for improving the light absorption rate with a spectral sensitizing dye, particularly a technique for multilayer adsorption of a sensitizing dye. Multilayer adsorption means that more dye chromophore is adsorbed (or laminated) on the surface of silver halide grains.
Specifically, for example, by utilizing intermolecular force, the sensitizing dye is adsorbed to the surface of the silver halide grain more than the saturated coating amount, or two or more separately unconjugated dye chromophores are shared. Examples include dyes linked by a bond, a so-called method of adsorbing so-called linked dyes to silver halide grains, and the like, which are described in the following multilayer adsorption-related patents.

JP 10-239789, JP 11-133531, JP 2000-267216, JP 2000-275772, JP 2001-75222, JP 2001-75247, JP 2001-75221, Special JP 2001-75226, JP 2001-75223, JP 2001-255615, JP 2002-23294, JP 10-171058, JP 10-186559, JP 10-197980, JP JP 2000-81678, JP 2001-5132, JP 2001-166413, JP 2002-49113, JP 64-91134, JP 10-110107, JP 10-171058, JP JP 10-226758, JP 10-307358, JP 10-307359, JP 10-310715, JP 2000-231174, JP 2000-231172, JP 2000-231173, JP 2001 -356442, European Patent No. 985965A, European Patent No. 985964A, European Patent No. 985966A, European Patent No. 985967A, European Patent No. 1085372A, European Patent No. 1085373A, European Patent No. 1172688A, European Patent No. 1199595A No., European Patent No. 887700A1.
Furthermore, it is preferable to use in combination with the techniques described in the patents disclosed in JP-A-10-239789, JP-A-2001-75222, and JP-A-10-171058.

Various dye forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferred.
Yellow couplers: couplers represented by formulas (I) and (II) in European Patent Application Publication 502,424A; couplers represented by Formulas (1) and (2) in European Patent Application Publication 513,496A (particularly Y-28 on page 18) A coupler represented by formula (I) in claim 1 of European Patent Application 568,037A; a coupler represented by general formula (I) in lines 45 to 55 of column 1 of US Pat. No. 5,066,576; paragraph of JP-A-4-74425 A coupler represented by the general formula (I) of 0008; a coupler described in claim 1 on page 40 of European Patent Application Publication No. 498,381A1 (particularly D-35 on page 18); a formula on page 4 of European Patent Application Publication No. 447,969A1 ( Y) (particularly Y-1 (page 17), Y-54 (page 41)); US Pat. No. 4,476,219, column 7, lines 36 to 58, couplers represented by formulas (II) to (IV) (Particularly II-17, 19 (column 17), II-24 (column 19)).

  Magenta coupler: JP-A-3-9737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 [A-4] -63 ( 134), (A-4) -73, -75 (page 139); M-4, -6 (page 26), M-7 (page 27) of EP 486,965; European Patent Application Publication 571,959A, M- 45 (page 19); JP-A-5-204106, (M-1) (page 6); JP-A-4-362631, paragraph 0237, M-22.

Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35) of JP-A-4-43345, 34 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.

As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B, DE 3,234,533 are preferable.
A coupler for correcting unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of European Patent Application Publication EP456,257A1 ( In particular, YC-86 on page 84), yellow colored magenta coupler ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the EP, and magenta colored magenta described in US Pat. Cyan coupler CC-9 (column 8), CC-13 (column 10), U.S. Pat. No. 4,837,136 (2) (column 8), colorless masking coupler represented by formula (A) of claim 1 of WO92 / 11575 (Especially exemplified compounds on pages 36 to 45) are preferable.

  Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of European Patent Application Publication No. 378,236A1 (especially T-101 (page 30), T- 104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), described in European Patent Application Publication 436, 938A2 on page 7. Compounds of formula (I) (especially D-49 (page 51)), European patent application publication 568,037A of formula (1) (especially (23) (page 11)), European patent application publication Compounds represented by formulas (I), (II) and (III) described on pages 5-6 of 440,195A2 (especially I- (1) on page 29); Bleach accelerator releasing compounds: European Patent Application Publication 310,125A2 Compounds represented by formulas (I) and (I ′) on page 5 (particularly (60) and (61) on page 1) and compounds represented by formula (I) in claim 1 of JP-A-6-59411 ( (7) (page 7); Ligand-releasing compound: Compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuko dye release Compound: Compounds 1-6 of columns 3-8 of US Pat. No. 4,749,641; fluorescent dye releasing compounds: compounds represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (especially compounds 1-11 of columns 7-10); development acceleration Or compound release compounds: compounds of formula (1), (2), (3) in column 3 of US Pat. No. 4,656,123 (especially (I-22) of column 25) and European Patent Application 450,637A2 ExZK-2 on page 36, lines 36 to 38; a compound that releases a group that becomes a pigment only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially Y-1 in columns 25 to 36) ~ Y-19).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: JP-A 62-215272, P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140-144) Latex for impregnation with oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger for developing agent: Compound represented by formula (I) in columns 2 to 54 of US Pat. (1), (2), (6), (12) (columns 4-5), US Pat. No. 4,923,787, column 2, line 5-10 formula (especially compound 1 (column 3); stain inhibitor: European patent Published application 298321A, page 4, lines 30 to 33, formulas (I) to (III), especially I-47,72, III-1,27 (pages 24 to 48); antifading agent: European patent application 298321A A -6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (pages 69-118), US5,122,444 columns 25-38 II-1 to III-23, in particular III-10, European Patent Application Publication No. 471347A, pages 8 to 12, I-1 to III-4, in particular II-2, US Patent 5,139,931, columns 32 to 40, A-1 to 48, especially A-39,42; color enhancers or blends Materials that reduce the use of color inhibitors: European Patent Application Publication No. 411324A, pages 5-24, I-1 to II-15, especially I-46; Formalin Scavenger: European Patent Application Publication No. 477932A, pages 24 to 29, SCV -1 to 28, in particular SCV-8; hardener: H-1,4,6,8,14 on page 17 of JP 1-214845, U.S. Pat. XII) (H-1 to 54), JP-A-2-148852, page 8 at the lower right, formula (6) (H-1 to 76), particularly H-14, US Pat. No. 3,325,287. Compound described in claim 1; Development inhibitor precursor: P-24,37,39 (pages 6-7) of JP-A-62-168139; compound described in claim 1 of US Pat. 29; Preservatives, fungicides: US Patent 4,923,790, columns 3-15, I-1 to III-43, especially II-1,9,10,18, III-25; Stabilizer, antifoggant: US patent 4,923,793, columns 6-16, I-1 to (14), especially I-1,60, (2), (13), U.S. Patent 4,952,483, columns 25-32, compounds 1-65, 36: Chemical sensitizer: Triphenylphosphine selenide, compound 50 of JP-A-5-40324; Dye: a-1 to b-20, especially a-1,12,18, pages 15-18 of JP-A-3-156450 , 27,35,36, b-5, 27-29 pages V-1 to 23, especially V-1, European Patent Application Publication 445627A, pages 33 to 55, FI-1 to F-II-43, especially FI -11, F-II-8, European Patent Application Publication No. 457153A, pp. 17-28, III-1 to 36, especially III-1,3, WO 88/04794, 8 to 26, Dye-1 to 124, microcrystals Dispersions, compounds 1-22 on pages 6-11 of European Patent Application 319999A, in particular compounds 1, compounds D-1 to 87 (3-28) of formula (1) to (3) of European Patent Application Publication 519306A Page 1), compounds 1 to 22 represented by formula (I) in U.S. Pat.No. 4,268,622 (columns 3 to 10), compounds (1) to (31) represented by formula (I) in U.S. Pat. UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) in JP-A-46-3335, represented by formula (I) in European Patent Application Publication No. 520938A Compounds (3) to (66 ) (Pages 10 to 44) and compound HBT-1 to 10 (page 14) represented by formula (III), compounds (1) to (31) represented by formula (1) of European Patent Application Publication No. 521823A (column 2) ~ 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper. Moreover, it is suitable for the lens-equipped film unit described in JP-B-2-32615 and JP-B-3-39784.
Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, RD. ing.

  The specific photographic sensitivity in the present invention is determined by the method described in JP-A-63-236035. This measuring method is in accordance with JIS K 7614-1981. The difference is that the development processing is completed within 30 minutes to 6 hours after exposure for sensitometry, and the development processing is based on Fuji Color Standard Processing Formula CN-16. In the point. Others are substantially the same as the measurement method described in JIS.

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the photographic light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed at 30 ° C for 3 minutes and 15 seconds with a color developer is the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.
The light-sensitive material of the present invention is prepared by the conventional methods described in the above-mentioned RD. No. 17643, pages 28 to 29, RD. It can be developed.

  Next, the processing liquid for the color negative film used in the present invention will be described.

  As the color developer used in the present invention, compounds described in JP-A-4-21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used. In particular, as a color developing agent for rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-Hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

  These color developing agents are preferably used in an amount of 0.01 to 0.08 mol, particularly 0.015 to 0.06 mol, more preferably 0.02 to 0.05, per liter of color developer (hereinafter, “L” is also expressed as “L”). It is preferably used in a molar range. The color developer replenisher preferably contains 1.1 to 3 times the color developing agent of this concentration, and more preferably 1.3 to 2.5 times.

Hydroxylamine can be widely used as a color developer preservative, but if higher preservability is required, it has a substituent such as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. Hydroxylamine derivatives are preferred, specifically N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine preferable. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one or more in place of hydroxylamine.
The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. Further, in the replenisher, as in the case of the color developing agent, it is preferable to contain a preservative at a concentration 1.1 to 3 times that of the mother liquor (processing tank solution).

In the color developer, sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol. In the replenisher, it is preferably used at a concentration of 1.1 to 3 times these.
The pH of the color developer is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher should be set to a high value in the range of 0.1 to 1.0 from these values. preferable. In order to stably maintain such pH, known buffering agents such as carbonate, phosphate, sulfosalicylate, and borate are used.
The replenishment amount of the color developer is also expressed as 80 to 1300 mL per 1 m ² of the photosensitive material. ) Is preferable, but from the viewpoint of reducing the environmental pollution load, a smaller amount is preferable, specifically 80 to 600 mL, more preferably 80 to 400 mL.

The bromide ion concentration in the color developer is usually 0.01 to 0.06 mol per liter, but for the purpose of suppressing fog and improving discrimination while maintaining sensitivity, and improving graininess. It is preferable to set to 0.015 to 0.03 mol per liter. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferable that the replenisher does not contain bromide ions.
C = A-W / V
C: Concentration of bromide ions in the color developer replenisher (mol / L)
A: Bromide ion concentration in target color developer (mol / L)
W: The amount (mole) of bromide ions eluted from the photosensitive material into the color developer when the photosensitive material of 1 m ² is color-developed.
V: Replenishment amount of color developer replenisher for 1m ² photosensitive material (L)

  In addition, when the replenishment amount is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone is used. It is also preferable to use development accelerators such as thioether compounds typified by pyrazolidones represented by representatives and 3,6-dithia-1,8-octanediol.

  The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof are those described in JP-A-5-72694 and JP-A-5-17312, particularly 1,3-diaminopropanetetraacetic acid, JP-A-5 A ferric complex salt of the compound of Example 1 on page 7 of No. 173312 is preferred.

  In order to improve the biodegradability of the bleaching agent, the compound ferric complex described in JP-A-4-25145, JP-A-4-268552, European Patent Application Publications 588,289, 591,934, JP-A-6-208213 is used as a bleaching agent. It is preferable to use as. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of the liquid having bleaching ability, and is preferably designed to be 0.1 to 0.15 mol for the purpose of reducing the discharge amount to the environment. Moreover, when the liquid which has bleaching ability is a bleaching liquid, it is preferable to contain 0.2-1 mol of bromide per liter, and it is preferable to contain 0.3-0.8 mol especially.

The replenisher for the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the density | concentration in mother liquid can be maintained constant.
C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P
C _R : Concentration of components in replenisher C _T : Concentration of components in mother liquor (processing tank solution) C _P : Concentration of components consumed during processing V ₁ : Replenishment with bleaching ability for 1 m ² photosensitive material Liquid replenishment volume (mL)
V ₂ : Amount brought in from the previous bath by 1m ² photosensitive material (mL)

In addition, it is preferable to contain a pH buffer in the bleaching solution, and it is particularly preferable to contain a dicarboxylic acid with little odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. It is also preferable to use known bleaching accelerators described in JP-A-53-95630, RD No. 17129, and US Pat. No. 3,893,858.
The bleaching solution is preferably replenished with 50 to 1000 mL of bleach replenisher per 1 m ² of the light-sensitive material, particularly preferably 80 to 500 mL, and more preferably 100 to 300 mL. Furthermore, it is preferable to aerate the bleaching solution.

For the processing solution having fixing ability, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied.
In particular, in order to improve the fixing speed and the preservability, the compounds represented by general formulas (I) and (II) of JP-A-6-301169 are incorporated into a processing solution having fixing ability alone or in combination. It is preferable. Use of sulfinic acid described in JP-A-1-224762 as well as p-toluenesulfinate is also preferable in terms of improving the preservability.

It is preferable to use ammonium as a cation from the viewpoint of improving desilvering property in a solution having bleaching ability or a solution having fixing ability, but it is preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .
In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309059.

The replenishing amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 mL, preferably 150 to 700 mL, particularly preferably 200 to 600 mL per 1 m ² of the photosensitive material.
In the bleach-fixing or fixing step, it is preferable to collect various silver recovery devices in-line or offline to recover silver. By installing in-line, the silver concentration in the liquid can be reduced and processed, so that the replenishment amount can be reduced. It is also preferable to recover silver offline and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-pipe to be a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and it is preferable that the ratio of the processing time in the front tank and the rear tank is in the range of 0.5: 1 to 1: 0.5. The range of 0.8: 1 to 1: 0.8 is particularly preferable.
In the bleach-fixing solution and the fixing solution, it is preferable that a free chelating agent that is not a metal complex is present from the viewpoint of improving the preservability. It is preferred to use a chelating agent.

  Regarding the water washing and stabilization step, the contents described in JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular, in place of formaldehyde, azolylmethylamines described in European Patent Applications 504,609 and 519,190 and N-methylolazoles described in JP-A-4-362943 are used in place of formaldehyde, and magenta couplers are used as stabilizers. It is preferable from the viewpoint of maintenance of the working environment that the surfactant liquid does not contain an image stabilizer such as formaldehyde after being equivalent.

  In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 mL per 1 m ² of the light-sensitive material, particularly 100 to 500 mL, and more preferably 150 to 300 mL, both for ensuring washing function and stabilizing waste and reducing waste for environmental conservation. To a preferable range. In such a replenishing amount, known methods such as thiabendazole, 1,2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one are used to prevent the growth of bacteria and sputum. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, an ion exchange resin or the like. It is more effective to use deionized water together with antibacterial agents and antibiotics.
In addition, the amount of replenishment of the water in the water washing or stabilizing liquid tank is reduced by performing reverse osmosis membrane treatment described in JP-A-3-46652, 3-53246, 3-355542, 3-121448, and 3-12030. The reverse osmosis membrane in this case is preferably a low pressure reverse osmosis membrane.

  In the processing in the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure No. 94-4992. In particular, a method of correcting using the temperature and humidity information of the developing machine installation environment based on (Formula-1) on the second page is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing, in which case deionized water is preferably used as the washing replenishment water.

As the treating agent used in the present invention, those described in the third page, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. Moreover, as a developing machine used for this, the film processor as described in the 22nd line to the 28th line of the 3rd page right column is preferable.
Specific examples of a processing agent, an automatic processor, and an evaporation correction method that are preferable for carrying out the present invention are described from the fifth page, right column, line 11 to the seventh page, right column, last line of the above published technical bulletin. .
The treatment agent used in the present invention may be supplied in any form, such as a solution in the concentration or concentrated form of the working solution, or granules, powders, tablets, pastes, and emulsions. Examples of such treatment agents include a liquid agent stored in a low oxygen permeable container in JP-A-63-17453, powders or granules in vacuum packaging in JP-A-4-19655 and 4-230748, 4- 221951 discloses granules containing a water-soluble polymer, JP-A-51-61837, JP-A-6-102628 discloses tablets, and JP-A-57-500485 discloses paste-like treatment agents, both of which are preferred. Although it can be used, it is preferable to use a liquid prepared in advance at a concentration in the state of use from the viewpoint of convenience during use.
In a container for storing these treatment agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidized liquid such as a color developer, a low oxygen permeable material is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

  Next, the processing liquid for the color reversal film used in the present invention will be described.

  Regarding processing for color reversal film, publicly known technology No. 6 (April 1, 1991) published by Aztec Co., Ltd., page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, page 2 The contents are described in detail in the lines, and any of the contents can be preferably applied.

In the color reversal film processing, the image stabilizer is contained in the adjustment bath or the final bath. Examples of such image stabilizers include formaldehyde sodium bisulfite and N-methylol azoles in addition to formalin. From the viewpoint of working environment, sodium formaldehyde bisulfite or N-methylol azoles are preferable, and N-methylol is preferred. As the azole, N-methyloltriazole is particularly preferable. Further, the contents relating to the color developer, the bleaching solution, the fixing solution, the washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.
Examples of preferable processing agents for color reversal films including the above contents include East-6 Kodak E-6 processing agent and Fuji Photo Film Co., Ltd. CR-56 processing agent.

Next, the magnetic recording layer used in the present invention will be described.
The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co-coated ferromagnetic iron oxides such as Co-coated γFe ₂ O ₃ are preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-61032. Also, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-59911 and 5-81652 can be used.

  The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product polymer (cellulose) described in JP-A-4-19569. Derivatives, sugar derivatives, etc.) and mixtures thereof. The resin has a Tg of -40 ° C to 300 ° C and a mass average molecular weight of 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanates formed by condensation of these isocyanates, and the like, for example, are described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. The coating liquid described in 341436 and the like is preferable.

  The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. An abrasive of non-spherical inorganic particles in which at least one kind of particles has a Mohs hardness of 5 or more is preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. The binder used at this time can use the above-mentioned binders, and preferably the same binder as that of the magnetic recording layer. Photosensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874, and EP 466,130.

  Next, the polyester support preferably used in the present invention will be described. For details including the photosensitive material, treatment, cartridge, and examples described later, the published technical report, public technical number 94-6023 (Invention Association; 1994.3.15). .)It is described in. The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). It is also desirable to devise measures such as preventing knurling of the core part by imparting knurls to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.
This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Mitsubishi Chemical's Diaresin and Nippon Kayaku's Kayaset.

  Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the light-sensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the primer method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles, or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds.
The most preferred antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ and V ₂ O _5. The volume resistivity of the seed is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The particle size is 0.001 to 1.0 μm. Crystalline metal oxide or composite oxide thereof (Sb, P, B, In , S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof.
The addition amount to the photographic material is preferably 5 to 500 mg / m ^2, particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or composite oxide thereof to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. As a preferable slip property, the coefficient of dynamic friction is 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min for a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.
Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles, and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve the matting property, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm. )), Polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic.
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Furthermore, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The size of the patrone may be the same as the current 135 size. To reduce the size of the camera, it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

  Further, a cartridge that feeds a film by rotating a spool may be used in the present invention. Alternatively, the film leading end may be housed in the cartridge main body, and the film leading end may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film that has been developed. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.

  The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as AP system), manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film), NEXIA A, NEXIA F, A film that has been processed into an AP system format like NEXIA H (in order ISO 200/100/400) and stored in a special cartridge can be listed. These AP system cartridge films are used by being loaded into an AP system camera such as FUJIFILM's EPION series (such as EPION 300Z). The color photographic light-sensitive material of the present invention is also suitable for a lens-equipped film such as a super slim, which is a Fuji color photorun made by Fuji Film.

The film photographed by these is printed through the following process in the minilab system.
(1) Reception (carrying out the exposed cartridge film from the customer)
(2) Detach process (transfer film from cartridge to intermediate cartridge for development process)
(3) Film development
(4) Rear touch process (return developed negative film to original cartridge) (5) Print (C / H / P 3 type print and index print on color paper [preferably SUPER FA8 made by Fujifilm] Continuous automatic printing)
(6) Verification / shipping (Cartridge and index print are verified by ID number and shipped together with the print)
As these systems, Fuji Film Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and Fujifilm Digital Lab System Frontier are preferable. FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL are listed as minilab champion film processors, and the recommended processing chemicals are Fujicolor Justit CN-16L and CN-16Q. Examples of printer processors include PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A, and recommended processing chemicals are Fujicolor Justit CP-47L and CP-40FAII. In Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer LP-1000W are used. The detacher used in the detaching process and the rear toucher used in the rear touching process are preferably DT200 / DT100 and AT200 / AT100 made by FUJIFILM respectively.

  The AP system can also be enjoyed with a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, you can load Aladdin 1000 directly with developed AP system cartridge film, or input image information of negative film, positive film, and print using 35mm film scanner FE-550 or flat head scanner PE-550. Digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL using a light-fixing type thermal color printing method, a pictography 3000 using a laser exposure heat development transfer method, or by an existing laboratory equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, you can enjoy photos on a TV simply by loading the developed AP system cartridge film into the Fujifilm photo player AP-1, and if you load it into the Fujifilm photo scanner AS-1, It is also possible to capture image information continuously at high speed. In addition, FUJIFILM Photo Vision FV-10 / FV-5 can be used to input film, prints or three-dimensional objects into a personal computer. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R or hard disk can be processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, Fujifilm's digital color printer NC-2 / NC-2D using the light fixing type thermal color printing method is suitable.
To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferred.

[Example]
Examples of the present invention are shown below. However, the present invention is not limited to this example.

The support used in this example was produced 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 2.66 × 10 Pa, an H ₂ O partial pressure of 75% in an atmospheric gas, a discharge frequency of 30 kHz on each of both surfaces. Glow discharge treatment was performed at an output of 2500 W and 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 at a coating amount of 5 mL / m ² using the bar coating method described in JP-B-58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate 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 subjected to a heat treatment at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours to carry out an annealing treatment and then support. 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

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

2) Second layer (transparent magnetic recording layer)
[1] 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 / 4G sand mill) at 2000 rpm for 4 hours. As media, 1 mmφ glass beads were used.

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.
[2] 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 [dispersion a] Sumicorundum AA-1.5 152 g
Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) 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 media, 1 mmφ zirconia beads were used.
(B) Colloidal silica particle dispersion [dispersion b] (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%.

[3] 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 particle dispersion “MEK-ST” [dispersion b] 128 g
(Solid content 30%)
AA-1.5 particle 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)
[1] Preparation of Sliding Agent Dispersion Stock Solution The following solution A was heated and dissolved at 100 ° C., added to solution A, and then dispersed with a high-pressure homogenizer to prepare a dispersing agent dispersion stock solution.
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

[2] 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 Silicone)
Compound _{1-1: (CH 3 O) 3} Si- (CH 2) 3 -NH 2)
5.53 parts by mass Compound 1 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.
Diacetone alcohol 252.93 parts by mass The above liquid was dispersed for 3 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON Co., Ltd.)” while cooling with ice and stirring to complete a spherical inorganic particle dispersion c1.

[3] Preparation of spherical organic polymer particle dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.
XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass Methyl ethyl ketone 120 parts by mass Cyclohexanone 120 parts by mass (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.

[4] Preparation of third layer coating solution The above was added to the above-mentioned 542 g of the lubricant dispersion stock solution to obtain a third layer coating solution.
Diacetone alcohol 5950 g
Cyclohexanone 176 g
Ethyl acetate 1700 g
The spherical inorganic particle 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 Chemi 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, on the opposite side to the support of the back layer obtained above, each layer having the following composition was applied in layers to prepare a color negative film sample 101.
(Composition of photosensitive layer)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

(Sample 101)
First layer (first antihalation layer)
Black colloidal silver Silver 0.125
Silver iodobromide emulsion grains having an average grain size of 0.07 μm Silver 0.01
Gelatin 0.922
ExM-1 0.068
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
F-8 0.001
HBS-1 0.050
HBS-2 0.002

Second layer (second antihalation layer)
Black colloidal silver Silver 0.052
Gelatin 0.420
ExF-1 0.002
F-8 0.001
Solid disperse dye ExF-7 0.122
HBS-1 0.076

Third layer (intermediate layer)
ExC-2 0.050
Cpd-1 0.090
Polyethyl acrylate latex 0.200
HBS-1 0.100
Gelatin 0.700

4th layer (low sensitivity red sensitive emulsion layer)
Em-D Silver 0.503
Em-C Silver 0.343
ExC-1 0.190
ExC-2 0.013
ExC-3 0.070
ExC-4 0.121
ExC-5 0.010
ExC-6 0.007
ExC-8 0.053
ExC-9 0.020
Cpd-2 0.025
Cpd-4 0.025
Cpd-7 0.015
UV-2 0.047
UV-3 0.086
UV-4 0.018
HBS-1 0.240
HBS-5 0.038
Gelatin 0.994

5th layer (medium sensitivity red emulsion layer)
Em-B Silver 0.490
Em-C Silver 0.455
ExC-1 0.159
ExC-2 0.072
ExC-3 0.020
ExC-4 0.104
ExC-5 0.023
ExC-6 0.010
ExC-8 0.016
ExC-9 0.005
Cpd-2 0.036
Cpd-4 0.028
Cpd-7 0.020
HBS-1 0.129
Gelatin 0.890

6th layer (high-sensitivity red-sensitive emulsion layer)
Em-A Silver 1.110
ExC-1 0.245
ExC-3 0.035
ExC-6 0.025
ExC-8 0.114
ExC-9 0.022
ExY-3 0.010
Cpd-2 0.066
Cpd-4 0.079
Cpd-7 0.030
HBS-1 0.329
HBS-2 0.120
Gelatin 1.240

7th layer (intermediate layer)
Cpd-1 0.094
Cpd-6 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 0.177
Em-K Silver 0.170
Cpd-4 0.034
ExM-2 0.144
ExM-3 0.014
ExY-1 0.018
ExY-4 0.036
ExC-7 0.026
HBS-1 0.218
HBS-3 0.003
HBS-5 0.030
Gelatin 0.614

9th layer (low sensitivity green emulsion layer)
Em-H Silver 0.330
Em-G Silver 0.335
Em-I Silver 0.082
ExM-2 0.374
ExM-3 0.045
ExY-1 0.018
ExC-7 0.007
HBS-1 0.098
HBS-3 0.010
HBS-4 0.074
HBS-5 0.544
Cpd-5 0.010
Cpd-7 0.020
Gelatin 1.465

10th layer (medium sensitive green sensitive emulsion layer)
Em-F Silver 0.459
ExM-2 0.057
ExM-3 0.028
ExY-3 0.008
ExC-6 0.010
ExC-7 0.011
ExC-8 0.010
HBS-1 0.064
HBS-3 0.002
HBS-4 0.020
HBS-5 0.020
Cpd-5 0.004
Cpd-7 0.010
Gelatin 0.443

11th layer (high sensitivity green emulsion layer)
Em-E silver 0.788
ExC-6 0.002
ExC-8 0.012
ExM-1 0.014
ExM-2 0.033
ExM-3 0.033
ExY-3 0.007
Cpd-3 0.004
Cpd-4 0.007
Cpd-5 0.010
Cpd-7 0.020
HBS-1 0.144
HBS-3 0.003
HBS-4 0.020
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.930

12th layer (yellow filter layer)
Cpd-1 0.098
Solid disperse dye ExF-2 0.070
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-6 0.010
HBS-1 0.049
Gelatin 0.626

13th layer (low sensitivity blue-sensitive emulsion layer)
Em-O Silver 0.108
Em-M Silver 0.324
Em-N Silver 0.242
ExC-1 0.022
ExC-7 0.015
ExY-1 0.002
ExY-2 0.895
ExY-4 0.056
Cpd-2 0.102
Cpd-3 0.004
HBS-1 0.225
HBS-5 0.070
Gelatin 1.550

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-L Silver 0.720
ExY-2 0.205
ExY-3 0.008
ExY-4 0.070
Cpd-2 0.074
Cpd-3 0.001
Cpd-7 0.030
HBS-1 0.120
Gelatin 0.680

15th layer (first protective layer)
Silver iodobromide emulsion grains having an average grain size of 0.07 μm silver 0.305
UV-1 0.211
UV-2 0.132
UV-3 0.198
UV-4 0.026
F-11 0.009
S-1 0.086
HBS-1 0.175
HBS-4 0.050
Gelatin 1.986

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

Furthermore, in order to improve storage stability, processability, pressure resistance, antibacterial / antibacterial properties, antistatic properties and coatability as appropriate for each layer, W-1 to W-6, B-4 to B-6, F-1 thru | or F-19 and lead salt, platinum salt, iridium salt, and rhodium salt are contained.
Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the 12th layer was dispersed by the following method.
ExF-2 wet cake (including 17.6% by weight 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 dispersions of ExF-4 and ExF-7 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.

The silver halide grains contained in the emulsions Em-A to O are all silver iodobromide grains.
In Table 1, emulsions Em-A to C are added with an optimal amount of spectral sensitizing dyes 1 to 3, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsions Em-E to G are added with an optimal amount of spectral sensitizing dyes 4 to 6, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized.
Emulsion Em-J is added with an optimal amount of spectral sensitizing dyes 7 and 8, and is optimally gold sensitized, sulfur sensitized and selenium sensitized. Emulsion Em-L is added with an optimal amount of spectral sensitizing dyes 9 to 11, and is optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsion Em-O is added with an optimal amount of spectral sensitizing dyes 10 to 12, and is optimally gold sensitized and sulfur sensitized. Emulsions Em-D, H, I, K, M, and N are added with an optimum amount of spectral sensitizing dyes listed in Table 2, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized.

  The sensitizing dyes used in the examples of the present invention are shown below.

For the preparation of tabular grains, low molecular weight gelatin is used according to the examples described in JP-A-1-158426.
Emulsions Em-A to K contain optimum amounts of Ir and Fe.
Emulsions Em-L to O are reduction sensitized during grain preparation.
When a high-voltage electron microscope is used for the tabular grains, dislocation lines as described in JP-A-3-237450 are observed.
In the emulsions Em-A to C and J, dislocation was introduced using an iodide ion releasing agent in accordance with the examples described in JP-A-6-11787.
Emulsion Em-E was introduced with dislocations using silver iodide fine grains prepared immediately before addition in another chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570.
Hereinafter, other compounds used in Examples of the present invention will be shown.

  The above silver halide color photographic light-sensitive material is referred to as Sample 101.

(Preparation of samples 102 to 104)
Samples 101 were prepared in the same manner as Sample 101 except that the compound of the present invention was added by emulsifying and dispersing the sixth layer, the eleventh layer, and the fourteenth layer of Sample 101 as shown in Table 3.
Samples 101 to 104 were exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

The exposed sample was processed by the method described below.
(Processing method)
Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C
White 3 minutes 00 seconds 38 ℃
Washing with water 30 seconds 24 ℃
3 minutes 00 seconds 38 ℃
Washing with water (1) 30 seconds 24 ℃
Washing with water (2) 30 seconds 24 ℃
Stable 30 seconds 38 ℃
Dry 4 min 20 sec 55 ° C

Next, the composition of the treatment liquid will be described.
(Color developer) (Unit: g)
Diethylenetriaminepentaacetic acid 1.0
1-hydroxyethylidene-1,1-diphosphonic acid 2.0
Sodium sulfite 4.0
Potassium carbonate 30.0
Potassium bromide 1.4
Potassium iodide 1.5mg
Hydroxylamine sulfate 2.4
4- [N-ethyl-N- (β-hydroxyethyl) amino]-
2-Methylaniline sulfate 4.5
Add water and add 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) (Unit: g)
Ethylenediaminetetraacetic acid sodium ferric acid trihydrate 100.0
Ethylenediaminetetraacetic acid disodium salt 10.0
3-mercapto-1,2,4-triazole 0.03
Ammonium bromide 140.0
Ammonium nitrate 30.0
Aqueous ammonia (27%) 6.5 mL
Add water and add 1.0L
pH (adjusted with ammonia water and nitric acid) 6.0

(Fixing solution) (Unit: g)
Ethylenediaminetetraacetic acid disodium salt 0.5
Ammonium sulfite 20.0
Ammonium thiosulfate aqueous solution (700 g / L)
295.0 mL
Acetic acid (90%) 3.3
Add water and add 1.0L
pH (adjusted with aqueous ammonia and nitric acid) 6.7

(Stabilizer) (Unit: g)
p-nonylphenoxypolyglycidol (average glycidol polymerization degree 10) 0.2
Ethylenediaminetetraacetic acid 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazol-1-ylmethyl)
Piperazine 0.75
Hydroxyacetic acid 0.02
Hydroxyethyl cellulose 0.1
(Daicel Chemical HEC SP-2000)
1,2-benzisothiazolin-3-one 0.05
Add water and add 1.0L
pH 8.5

The sensitivity of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer is represented by the logarithm of the reciprocal of the exposure amount at which the cyan, magenta, and yellow color image densities give the minimum density +0.2, respectively, and is represented by the difference from the sample 101.
Graininess was evaluated by determining the RMS granularity of cyan, magenta, and yellow color images 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.

Comparative compound A is described in [Chemical Formula 35].
As described above, it is clear that the method of the present invention is an excellent method for obtaining an image with high sensitivity without impairing the graininess. Further, it can be seen that the method of using the compound of the present invention for the red-sensitive layer and the blue-sensitive layer has a greater effect of increasing the sensitivity than the method of using the compound for the green-sensitive layer.

  A sample 201 was prepared in the same manner as the sample 103 except that the compound (A-1) used in the 11th layer of the sample 103 described in Example 1 was moved from the 11th layer to the 12th layer.

When this sample was evaluated in the same manner as Sample 103 by the method described in Example 1, the sensitivity increasing effect of the green sensitive layer was 0.08, which was lower than 0.11 of Sample 103. However, when the sample is prepared after the coating solution of the 11th layer and the 12th layer is aged for 12 hours at 40 ° C., the fog of the 11th layer rises in the case of the sample 103, but it is not preferable. A favorable result was obtained without being seen.
It was found that adding the compound of the present invention directly to the photosensitive layer is preferable from the viewpoint of increasing the effect, but it is preferable to add it to the adjacent non-photosensitive layer from the viewpoint of preventing side effects as described above.

The support used in this example was produced by the same method as in Example 1.
Next, on the opposite side of the backing layer support obtained above, each layer having the following composition was applied in layers to prepare a color negative film sample 301.
(Composition of photosensitive layer)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.
The compound numbers used are shown in common with Example 1.

(Sample 301)
First layer (first antihalation layer)
Black colloidal silver Silver 0.104
Silver iodobromide emulsion grains having an average grain size of 0.07 μm Silver 0.011
Gelatin 0.910
ExM-1 0.060
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
F-8 0.001
HBS-1 0.050
HBS-2 0.002

Second layer (second antihalation layer)
Black colloidal silver Silver 0.055
Gelatin 0.413
ExF-1 0.002
F-8 0.001
Solid disperse dye ExF-7 0.120
HBS-1 0.076

Third layer (intermediate layer)
ExC-2 0.050
Cpd-1 0.090
Polyethyl acrylate latex 0.200
HBS-1 0.100
Gelatin 0.700

4th layer (low sensitivity red sensitive emulsion layer)
Em-C 'Silver 0.515
Em-D 'Silver 0.344
ExC-1 0.193
ExC-2 0.010
ExC-3 0.073
ExC-4 0.120
ExC-5 0.010
ExC-6 0.007
ExC-8 0.053
ExC-9 0.020
Cpd-2 0.020
Cpd-4 0.025
Cpd-7 0.015
UV-2 0.047
UV-3 0.086
UV-4 0.018
HBS-1 0.240
HBS-5 0.038
Gelatin 0.994

5th layer (medium sensitivity red emulsion layer)
Em-B 'Silver 0.943
ExC-1 0.145
ExC-2 0.076
ExC-3 0.023
ExC-4 0.100
ExC-5 0.023
ExC-6 0.010
ExC-8 0.016
ExC-9 0.005
Cpd-2 0.036
Cpd-4 0.028
Cpd-7 0.020
HBS-1 0.120
Gelatin 0.894

6th layer (high-sensitivity red-sensitive emulsion layer)
Em-A 'Silver 1.230
ExC-1 0.230
ExC-3 0.034
ExC-6 0.025
ExC-8 0.112
ExC-9 0.023
ExY-3 0.011
ExM-4 0.150
Cpd-2 0.062
Cpd-4 0.079
Cpd-7 0.030
HBS-1 0.329
HBS-2 0.120
Gelatin 1.300

7th layer (intermediate layer)
Cpd-1 0.094
Cpd-6 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-E 'Silver 0.355
Cpd-4 0.038
ExM-2 0.180
ExM-3 0.010
ExY-1 0.015
ExY-4 0.039
ExC-7 0.030
HBS-1 0.218
HBS-3 0.003
HBS-5 0.030
Gelatin 0.614

9th layer (low sensitivity green emulsion layer)
Em-I 'Silver 0.300
Em-J 'Silver 0.360
Em-H 'Silver 0.049
ExM-2 0.365
ExM-3 0.044
ExY-1 0.013
ExC-7 0.007
HBS-1 0.098
HBS-3 0.010
HBS-4 0.074
HBS-5 0.544
Cpd-5 0.010
Cpd-7 0.020
Gelatin 1.464

10th layer (medium sensitive green sensitive emulsion layer)
Em-G 'Silver 0.440
ExM-2 0.058
ExM-3 0.026
ExM-4 0.040
ExY-3 0.005
ExC-6 0.013
ExC-7 0.011
ExC-8 0.010
HBS-1 0.064
HBS-3 0.002
HBS-4 0.020
HBS-5 0.020
Cpd-5 0.004
Cpd-7 0.010
Gelatin 0.432

11th layer (high sensitivity green emulsion layer)
Em-F 'Silver 0.920
Em-H 'Silver 0.100
ExC-6 0.003
ExC-8 0.012
ExM-1 0.016
ExM-2 0.038
ExM-3 0.032
ExM-4 0.080
ExY-3 0.010
Cpd-3 0.004
Cpd-4 0.007
Cpd-5 0.010
Cpd-7 0.020
HBS-1 0.144
HBS-3 0.003
HBS-4 0.020
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.988

12th layer (yellow filter layer)
Cpd-1 0.098
Solid disperse dye ExF-2 0.070
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-6 0.010
HBS-1 0.049
Gelatin 0.626

13th layer (low sensitivity blue-sensitive emulsion layer)
Em-O 'Silver 0.111
Em-M 'Silver 0.320
Em-N 'Silver 0.211
ExC-1 0.020
ExC-7 0.015
ExY-1 0.002
ExY-2 0.355
ExY-4 0.050
ExY-5 0.430
Cpd-2 0.102
Cpd-3 0.004
HBS-1 0.225
HBS-5 0.070
Gelatin 1.450

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-K 'Silver 0.910
Em-L 'Silver 0.110
ExY-2 0.065
ExY-3 0.005
ExY-4 0.073
ExY-5 0.121
ExM-4 0.070
Cpd-2 0.074
Cpd-3 0.001
Cpd-7 0.030
HBS-1 0.124
Gelatin 0.699

15th layer (first protective layer)
Silver iodobromide emulsion grains having an average grain size of 0.07 μm silver 0.305
UV-1 0.211
UV-2 0.132
UV-3 0.198
UV-4 0.026
UV-5 0.200
F-11 0.009
S-1 0.086
HBS-1 0.175
HBS-4 0.050
Gelatin 2.120

16th layer (second protective layer)
H-1 0.400
B-1 (diameter 1.7 μm) 0.050
B-2 (diameter 1.7 μm) 0.150
B-3 0.050
S-1 0.200
Gelatin 0.750
Furthermore, in order to improve the preservability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coatability as appropriate for each layer, W-1 to W-11, B-4 to B-6, F-1 thru | or F-19 and lead salt, platinum salt, iridium salt, and rhodium salt are contained.

The emulsion is added with an optimal amount of spectral sensitizing dyes described in Table 7 and optimally gold sensitized, sulfur sensitized, and selenium sensitized.
The above silver halide color photographic light-sensitive material is referred to as Sample 301.

(Preparation of samples 302 to 304)
The sample 301 was prepared in the same manner as the sample 301 except that one compound of the present invention was added to the sixth layer, the eleventh layer, and the fourteenth layer of the sample 301 as shown in Table 8.
Samples 301 to 304 were exposed for 1/100 second through gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

The exposed sample was treated in the same manner as described in Example 1.
The sensitivity and graininess of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were the same as those described in Example 1.

  From the above results, it is apparent that the method of the present invention is an excellent method for obtaining an image with high sensitivity without impairing the graininess.

In Samples 101 to 104 in Table 3 of Example 1, a sensitizing dye was added to the halogenated emulsion of the blue-sensitive 14th layer, and then the following compound D-1 generating 2 electrons or more with one photon was added: Evaluation was conducted in the same manner except for the above. As a result, with respect to the sensitivity of the sample 101 to which D-1 was not added, the sample 101 to which D-1 was added was +0.35, 102 was +0.32, 103 was +0.53, and 104 was +0.55. Higher sensitivity could be obtained with the compound.
Further, in the samples 101 to 104 in Table 3 of Example 1, the following was added as the sensitizing dye of the blue-sensitive 14th layer halogenated emulsion, and the sensitizing dye was multilayer adsorbed in the same manner. evaluated. As a result, in contrast to the sensitivity of sample 101 not subjected to multilayer adsorption, sample 101 with multilayer adsorption of sensitizing dye is +0.08, 102 is +0.05, 103 is +0.25, and 104 is +0.27. Higher sensitivity could be obtained by multilayer adsorption.
Further, in Samples 101 to 104 in Table 3 of Example 1, the same sensitizing dye as described above was adsorbed on the blue-sensitive 14th layer of the halogenated emulsion, and then the compound D-1 was added. Evaluation was performed in the same manner. As a result, the sample 101 to which the sensitizing dye was multilayer-adsorbed and D-1 was added with respect to the sensitivity of the sample 101 that was not multilayer-adsorbed and D-1 was not added was +0.40, 102 was +0.34, 103 +0.80 and 104 were +0.85. By adding a compound that multi-layers adsorbed sensitizing dye and generates two or more electrons with one photon, higher sensitivity could be obtained.

Claims (6)

A silver halide photographic light-sensitive material containing a sensitizing dye and a compound having at least one aromatic hydrocarbon ring or aromatic heterocyclic ring, wherein the compound interacts with the sensitizing dye by attractive force during development; A silver halide photographic light-sensitive material, characterized in that the interaction is large enough to increase the photographic sensitivity of the light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material according to claim 1 is a silver halide color photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound is a compound having three or more aromatic hydrocarbon rings or aromatic heterocyclic rings. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (H), characterized in that the photographic sensitivity is increased as compared with the same light-sensitive material except that the compound is not contained. A silver halide photographic material.
Formula _{(H) A 1 - (X} 1) n 1 -B 1 - (X 2) n 2 -A 2 Mdmd
In the formula, A ₁ and A ₂ represent an aryl group or an aromatic heterocyclic group, B ₁ represents an atomic group having π electrons, and X ₁ and X ₂ represent a linking group. n ₁ and n _{2 each} represents 0 or 1; Md represents a charge balanced counter ion, and md represents a number of 0 or more necessary to neutralize the charge of the molecule. A method of increasing the photographic sensitivity of a silver halide photographic light-sensitive material with a compound having at least one aromatic hydrocarbon ring or aromatic heterocyclic ring having a property of interacting with a sensitizing dye during development. A method for increasing the photographic sensitivity of a silver halide photographic light-sensitive material by the compound represented by formula (H) according to claim 4.