JP2007264036A - Silver halide color photographic sensitive material for motion picture - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having processing stability and stability to temperature and humidity changes in exposure, and suitable for use as a color positive photosensitive material for a motion picture giving stable latent images. <P>SOLUTION: The silver halide color photographic sensitive material for a motion picture has red-, green- and blue-sensitive silver halide emulsion layers on a transmissive support, wherein at least one of the emulsion layers contains a silver halide emulsion having a silver chloride content of ≥95 mol%, the emulsion contains at least one specific metal complex represented, e.g., by [ReCl<SB>6</SB>]<SP>2-</SP>and at least one specific metal complex represented, e.g., by [IrCl<SB>5</SB>(H<SB>2</SB>O)]<SP>2-</SP>, and at least one specific compound represented, e.g., by formula (FS-1) is contained in the sensitive material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a silver halide color photographic light-sensitive material for movies which is stable in processing, stable against changes in temperature and humidity during exposure, and has a stable latent image.

  Movie, which is an application of silver halide photography, is a method of obtaining a moving image by sequentially projecting 24 dense still images per second, and has an overwhelming image quality compared to other methods of obtaining moving images. Have. However, recent rapid developments in electronic technology and information processing technology can propose simpler video playback means with image quality close to that of movies, such as a projector using a Texas Instruments DMD device or an ILA projector from Hughes JVC. It reached to. Therefore, the current situation is that there is a demand for even higher image quality, easier handling, and faster development processing (time reduction) for movies.

  Photosensitive materials (movie color positive film) used in movies, especially in the projection stage, are high quality because they are directly viewed by users through projectors, and large quantities because they are viewed in movie theaters around the world. There is a need for production, and it is required to speed up the development process and finish each with stable and uniform performance. First, with regard to speeding up of development processing, shortening the development time of silver halide photographic light-sensitive materials has been taken up as an important issue from the past. There have been many studies on possible treatment agents. In particular, the use of a silver halide emulsion having a high silver chloride content is an extremely effective means for rapid processing of color photographic light-sensitive materials (see, for example, Patent Document 1).

  Since movies are enlarged and projected at the time of projection, the photosensitive material used is required to have fine graininess. To improve graininess, techniques for using relatively small sized silver halide grains have been disclosed so far (see, for example, Patent Documents 2 to 4), and lowering the average grain size is an important factor for improving image quality. become.

On the other hand, for the purpose of obtaining a wide latitude, it is preferable to use a monodispersed emulsion of silver halide grains having different sensitivities blended in the same layer or to carry out multilayer coating.
For spectrally sensitized emulsions, the sensitivity of the emulsion is proportional to the surface area of the silver halide grains, so generally high-sensitivity emulsions use large-grain silver halide grains and low-sensitivity emulsions use grain size. Small silver halide grains. However, since the color positive film for movie currently used uses relatively small-sized silver halide grains from the viewpoint of the above graininess, it is further reduced in size using high-solubility silver chloride, It is not preferable to prepare a low-sensitivity emulsion because it is difficult to prepare stable and uniform grains, and variation due to processing is large. Although it is also known to reduce the sensitivity using a metal complex, the stability against changes in temperature and humidity during exposure and the stability of the latent image were insufficient.

U.S. Pat. No. 4,840,878 Japanese Patent Laid-Open No. 62-99751 JP-A-4-217242 JP-A-4-275544

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the present invention provides a silver halide color photographic light-sensitive material suitable as a color positive light-sensitive material for movies, which is stable in processing, stable against changes in temperature and humidity during exposure, and has a stable latent image. With the goal.

Means for solving the above problems are as follows.
(1) A silver halide color photographic light-sensitive material for cinema having a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a transmission type support, wherein at least one of the silver halide emulsion layers is A silver halide emulsion having a silver chloride content of 95 mol% or more is contained, and the silver halide emulsion contains at least one metal complex represented by the following general formula (D1) and the following general formula (D2). And a silver halide color photographic light-sensitive material for cinema, wherein the silver halide color photographic light-sensitive material contains at least one compound represented by the following general formula (FS).
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
(In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, X ^D1 represents a halogen ion. L ^D1 is an arbitrary different from X ^D1 Wherein n represents 3, 4, 5 or 6, and m represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+, where A plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different, provided that the metal complex represented by the general formula (D1) is a ligand. (There is no or no CN ion.)
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
(In the general formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, L ^D2 represents an arbitrary ligand different from X ^D2, and n represents 3, 4, or 5) , M is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2 may be the same or different from each other, If L ^D2 is present, these may be the same or different.)

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

(2) The metal complex represented by the general formula (D1) is contained in silver halide grains in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol per mol of silver (1) A silver halide color photographic light-sensitive material for movies described in 1.
(3) The metal complex represented by the general formula (D1) is a metal complex represented by the following general formula (D1A), or any one of (1) to (2) Silver halide color photographic material for movies.
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
(In the general formula (D1A), M ^D1A represents Re, Ru, Os or Rh, X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os; ^{When D1A} is Rh, it represents H ₂ O, OH or O. n represents 3, 4, 5 or 6, m is the charge of the metal complex, and 4-, 3-, 2-, 1-, Represents 0 or 1+, wherein a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different.

(4) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2A), described in any one of (1) to (3) Silver halide color photographic material for movies.
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
(In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), L ^D2A represents an arbitrary inorganic ligand different from X ^D2A , n is 3, 4 or 5 and m is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2A may be the same or different from each other ^Or when there are a plurality of L ^{D2A s} , these may be the same or different.)

(5) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2B), (1) to (3) Silver halide color photographic material for movies.
General formula (D2B)
[IrX ^D2B _n L ^D2B _(6-n) ] ^m
(In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or its base Represents a ligand in which a carbon or hydrogen atom in a part of the structure is replaced with another atom or atomic group, n represents 3, 4 or 5, m represents the charge of the metal complex, and 5-4 -, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2B may be the same or different from each other, and when a plurality of L ^D2B are present, they may be the same or different. .)

(6) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2C), described in any one of (1) to (3) Silver halide color photographic material for movies.
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
(In the general formula (D2C), X ^D2C represents a halogen ion or a pseudo-halogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand and contains at least one nitrogen atom in the ring skeleton. Represents a ligand containing at least one sulfur atom, and may have an optional substituent on a carbon atom in the ring skeleton, n represents 3, 4 or 5, and m represents the charge of the metal complex. 5-, 4-, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2Cs may be the same as or different from each other, and when a plurality of L ^D2Cs are present, May be the same or different.)

(7) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2D), and is described in any one of (1) to (3) Silver halide color photographic material for movies.
General formula (D2D)
[IrX ^D2D _n L ^D2D _(6-n) ] ^m
(In the general formula (D2D), X ^D2D represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2D is a 5-membered ring ligand and includes at least two nitrogen atoms in the ring skeleton. Represents a ligand containing at least one sulfur atom, and may have an optional substituent on a carbon atom in the ring skeleton, n represents 3, 4 or 5, and m represents the charge of the metal complex. 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2Ds may be the same as or different from each other, and when a plurality of L ^D2Ds are present, May be the same or different.)

(8) The silver halide color photographic photosensitive film for cinema according to any one of (1) to (7), wherein the silver halide emulsion grain has an average equivalent sphere size of 0.25 μm or less. material.

  According to the present invention, there is provided a silver halide color photographic light-sensitive material suitably used as a color positive light-sensitive material for movies, which has excellent graininess and processing stability, is stable against changes in temperature and humidity, and has a stable latent image. be able to.

The present invention is described in detail below.
First, the metal complex represented by the following general formula (D1) used in the present invention will be described. In addition, the metal complex represented by the general formula (D1) is a complex (high contrast complex) used to make the gradation of the photosensitive material high.
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D1 may be the same as or different from each other, and when there are a plurality of L ^D1 , these may be the same or different. However, the metal complex represented by the general formula (D1) does not have or has one CN ion as a ligand.

Among the metal complexes represented by the general formula (D1), a metal complex represented by the following general formula (D1A) is preferable.
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
In the general formula (D1A), M ^D1A represents Re, Ru, Os, or Rh, and X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, and represents H ₂ O, OH or O when M ^D1A is Rh. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different. X ^D1A has the same meaning as X ^{D1 in} formula (D1), and the preferred range is also the same.

Although the preferable specific example of a metal complex represented by general formula (D1) below is given, this invention is not limited to these.
[ReCl ₆ ] ^2-
[ReCl ₅ (NO)] ^2-
[RuCl ₆ ] ^2-
[RuCl ₆ ] ^3-
[RuCl ₅ (NO)] ^2-
[RuCl ₅ (NS)] ^2-
[RuBr ₅ (NS)] ^2-
[OsCl ₆ ] ^4-
[OsCl ₅ (NO)] ^2-
[OsBr ₅ (NS)] ^2-
[RhCl ₆ ] ^3-
[RhCl ₅ (H ₂ O)] ^2-
[RhCl ₄ (H ₂ O) ₂ ] ^-
[RhBr ₆ ] ^3-
[RhBr ₅ (H ₂ O)] ^2-
[RhBr ₄ (H ₂ O) ₂ ] ^-
[PdCl ₆ ] ^2- [PtCl ₆ ] ^2-
Among these, [OsCl ₅ (NO)] ²⁻ or [RhBr ₆ ] ³⁻ is particularly preferable.

The metal complex represented by the following general formula (D2) preferably used in the present invention will be described.
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
In the general formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2 represents an arbitrary ligand different from X ^D2 . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2 may be the same or different from each other, and when a plurality of L ^D2 are present, these may be the same or different.
In the above, the pseudohalogen (halogenoid) ion is an ion having properties similar to a halogen ion. For example, a cyanide ion (CN ⁻ ), a thiocyanate ion (SCN ⁻ ), a selenocyanate ion (SeCN ^−). ), Tellurocyanate ion (TeCN ⁻ ), azidodithiocarbonate ion (SCSN ₃ ⁻ ), cyanate ion (OCN ⁻ ), thunderate ion (ONC ⁻ ), azide ion (N ₃ ⁻ ) and the like.
X ^D2 is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride Particularly preferred are ions and bromide ions. L ^D2 is not particularly limited and may be an inorganic compound or an organic compound, and may be charged or uncharged, but may be an uncharged inorganic compound or organic compound. preferable.

Among the metal complexes represented by the general formula (D2), a metal complex represented by the following general formula (D2A) is preferable.
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2A represents an arbitrary inorganic ligand different from X ^D2A . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2A may be the same or different from each other, and when a plurality of L ^D2A are present, these may be the same or different.
X ^D2A has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2A is preferably water, OCN, ammonia, phosphine, or carbonyl, and particularly preferably water.

Among the metal complexes represented by the general formula (D2), the metal complex represented by the following general formula (D2B) is more preferable.
General formula (D2B)
[IrX ^D2B _n L ^D2B _(6-n) ] ^m
In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or its base structure Represents a ligand in which some carbon or hydrogen atoms are replaced by other atoms or atomic groups. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2B may be the same or different from each other, and when a plurality of L ^D2B are present, these may be the same or different.
X ^D2B has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2B represents a ligand in which a chain or cyclic hydrocarbon is a base structure, or a carbon or hydrogen atom in a part of the base structure is replaced with another atom or atomic group. Ions are not included. L ^D2B is preferably a heterocyclic compound. More preferably, it is a 5-membered ring compound, and among the 5-membered ring compounds, a compound containing at least one nitrogen atom and at least one sulfur atom in the 5-membered ring skeleton is more preferable.

Among the metal complexes represented by the general formula (D2B), a metal complex represented by the following general formula (D2C) is more preferable.
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand which represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. It's okay. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Cs may be the same as or different from each other, and when there are a plurality of L ^D2Cs , these may be the same or different.
X ^D2C has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. The substituent on the carbon atom in the ring skeleton in L ^D2C is preferably a substituent having a smaller volume than the n-propyl group. As a substituent, methyl group, ethyl group, methoxy group, ethoxy group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, formyl group, thioformyl group, hydroxy group, mercapto group, amino group, hydrazino group , An azido group, a nitro group, a nitroso group, a hydroxyamino group, a carboxyl group, a carbamoyl group, and a halogen atom (fluoro group, chloro group, bromo group, iodo group) are preferred.

Among the metal complexes of the general formula (D2C), a metal complex represented by the following general formula (D2D) is more preferable.
General formula (D2D)
[IrX ^D2D _n L ^D2D _(6-n) ] ^m
In the general formula (D2D), X ^D2D represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2D is a 5-membered ring ligand that represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and has an optional substituent on a carbon atom in the ring skeleton. It's okay. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Ds may be the same as or different from each other, and when a plurality of L ^D2Ds are present, these may be the same or different.
X ^D2D has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2D is preferably a compound having a thiadiazole skeleton, and a substituent other than hydrogen is preferably bonded to the carbon atom in the compound. Preferred substituents are halogen atoms (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group, chloroformyl group, mercapto group, methylthio group, thioformyl group, thiol Carboxy group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso Group, nitro group, hydrazino group, hydrazono group or azide group, more preferably halogen (fluorine, chlorine, bromine, iodine), chloroformyl group, sulfino group, sulfo group, sulfamoyl group, isocyano group, cyanato group, Isoshi Anato group, thiocyanato group, isothiocyanato group, hydroxyimino group, nitroso group, nitro group, or azido group. Of these, chlorine, bromine, chloroformyl group, isocyano group, cyanato group, isocyanato group and thiocyanato group are particularly preferable. n is preferably 4 or 5, and m is preferably 2- or 1-.

Although the preferable specific example of a metal complex represented by general formula (D2) below is given, this invention is not limited to these.
[IrCl ₅ (H ₂ O)] ^2-
[IrCl ₄ (H ₂ O) ₂ ] ^-
[IrCl ₅ (H ₂ O)] ^-
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ^3-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (OH)] ^2-
[IrCl ₄ (OH) ₂ ] ^-
[IrCl ₅ (O)] ^4-
[IrCl ₄ (O) ₂ ] ^5-
[IrCl ₅ (O)] ^3-
[IrCl ₄ (O) ₂ ] ^4-
[IrBr ₅ (H ₂ O)] ^2-
[IrBr ₄ (H ₂ O) ₂ ] ^-
[IrBr ₅ (H ₂ O)] ^-
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ^3-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (OH)] ^2-
[IrBr ₄ (OH) ₂ ] ^-
[IrBr ₅ (O)] ^4-
[IrBr ₄ (O) ₂ ] ^5-
[IrBr ₅ (O)] ^3-
[IrBr ₄ (O) ₂ ] ^4-
[IrCl ₅ (OCN)] ^3-
[IrBr ₅ (OCN)] ^3-
[IrCl ₅ (thiazole)] ^2-
[IrCl ₄ (thiazole) ₂ ] ^-
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ^2-
[IrBr ₄ (thiazole) ₂ ] ^-
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ^2-
[IrCl ₄ (5-methylthiazole) ₂ ] ^-
[IrBr ₅ (5-methylthiazole)] ^2-
[IrBr ₄ (5-methylthiazole) ₂ ] ^-
Among these, [IrCl ₅ (5-methylthiazole)] ^2- is particularly preferable.

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do.
Metal complex represented by the general formula (D1), preferably added 1 × 10 ^-6 mol 1 × 10 ^-11 mol per mol of silver in the grain formation, 1 × 10 from 1 × 10 ^-10 mol ^-6 mol is more preferable, and 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁷ mol is most preferable. Metal complex represented by the general formula (D2), preferably added 1 × 10 ^-3 mol 1 × 10 ^-10 mol per mol of silver in the grain formation, 1 × 10 from 1 × 10 ^-8 mol It is most preferable to add ^-5 mol.

  In the present invention, the above metal complex is preferably added with a solution dissolved and kept warm at pH 4.0 to 10.0 and 0 to 25 ° C. in order to prevent changes in valence and ligand.

  In the present invention, the above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or in other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the metal complex has been previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing the complex only inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but a hexacoordinate complex having Ir as a central metal, in which all six ligands are Cl, Br, or I, has a silver bromide concentration maximum. It is preferable to contain.

Next, the photographic layers of the silver halide color photographic light-sensitive material for movie projection of the present invention will be described.
The silver halide color photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material having a transmission type support, and a plurality of silver halide emulsion layers having substantially different color sensitivities are formed on the support. And a silver halide color photographic material having at least one photosensitive layer. The present invention can be applied to color photographic light-sensitive materials for general use such as color positive film and movie positive film and movie. In particular, it is preferably applied to a color positive photosensitive material for movies.

In the present invention, the number and order of the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer are not particularly limited. Each of the yellow, cyan and magenta color-sensitive photosensitive silver halide emulsion layers is composed of a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities, even if the photosensitive silver halide emulsion layer is composed of one photosensitive silver halide emulsion layer. It may be.
There is no restriction between the color developability and color sensitivity of each color-sensitive photosensitive silver halide emulsion layer. For example, a color developable light-sensitive silver halide emulsion layer has color sensitivity in the infrared region. It doesn't matter.

  Examples of typical layer order include a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye and / or black colloidal silver in order from the support, a yellow color-forming photosensitive silver halide emulsion layer, a non-photosensitive layer. Hydrophilic colloid layer (color mixing prevention layer), cyan color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing preventing layer), magenta color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic Colloidal layer (protective layer). However, depending on the purpose, the order of installation may be changed, or the number of photosensitive silver halide emulsion layers or non-photosensitive hydrophilic colloid layers may be increased or decreased.

The iron content (Fe) in the silver halide color photographic light-sensitive material of the present invention is mainly introduced by gelatin, intentionally doped emulsion grains, dyes, etc., but the Fe content in the light-sensitive material of the present invention is as follows. The Fe content must be 2 × 10 ⁻⁵ mol / m ² or less (preferably 1 × 10 ⁻⁸ to 2 × 10 ⁻⁵ mol / m ² ), and 8 × 10 ⁻⁶ mol / m 2. ² or less (preferably 1 × 10 ⁻⁸ to 8 × 10 ⁻⁶ mol / m ² ) is preferable, and 3 × 10 ⁻⁶ mol / m ² or less (preferably 1 × 10 ^{−8 to} 3 × 10 ⁻⁶ mol / m ² ). m ² ) is most preferred.

  In the present invention, gelatin is preferably used as the hydrophilic colloid. If necessary, other hydrophilic colloids can be used in place of gelatin at any ratio. Examples of these include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin or casein, cellulose derivatives (eg, hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate), saccharides such as sodium alginate and starch derivatives. And a wide range of synthetic polymers such as polyvinyl alcohol, partial acetal of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole.

  Examples of the silver halide grains used in the present invention include silver chloride, silver bromide, (iodo) silver chlorobromide, and silver iodobromide. In particular, in the present invention, silver chloride, silver chlorobromide, silver chloroiodide and silver chloroiodobromide having a silver chloride content of 95 mol% or more can be preferably used in order to speed up the development processing time. The silver halide grains in this emulsion are those having regular crystals such as cubes, octahedrons and tetradecahedrons, those having irregular crystal systems such as spheres and plates, twin planes, etc. Those having the above crystal defects or a composite system thereof may be used. Further, it is preferable to use tabular grains whose main plane is the (111) plane or the (100) plane in terms of speeding up color development and reducing processing color mixing. Regarding tabular high silver chloride emulsion grains having a principal plane of (111) plane or (100) plane, JP-A-6-138619, U.S. Pat. Nos. 4,399,215, 5,061,617, 5,320,938, 5,264,337, 5,292,632, 5,314,798, 5,413,904, International Publication WO94 / 22051 It can be prepared by the method disclosed in each gazette or specification of the issue.

  As the silver halide emulsion that can be used together in the present invention, a silver halide emulsion having an arbitrary halogen composition may be used. From the viewpoint of rapid processability, a salt (iodinated) salt having a silver chloride content of 95 mol% or more. Silver and silver (iodo) bromide are preferred, and silver halide emulsions having a silver chloride content of 95 mol% or more are preferred as in the emulsion used in the present invention.

  The sphere equivalent diameter of the silver halide grains constituting the silver halide emulsion used in the present invention is preferably 0.25 μm or less, more preferably 0.20 μm or less, and 0.18 μm or less. The lower limit is not particularly limited, but is usually 0.05 μm, preferably 0.10 μm or more. In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. Particles with a sphere equivalent diameter of 0.25 μm correspond to cubic particles with a side length of about 0.20 μm, particles with a sphere equivalent diameter of 0.20 μm correspond to cubic particles with a side length of about 0.16 μm, and sphere equivalent diameter of 0.18 μm. These particles correspond to cubic particles having a side length of about 0.14 μm.

  The emulsion used in the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation coefficient of the sphere equivalent diameter of all particles used in the present invention is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter.

  The silver halide emulsion used in the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used. The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced. For gold sensitization, a compound such as chloroauric acid or a salt thereof, gold thiocyanate or gold thiosulfate can be used. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. Is more preferable.

  Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and ibid. 18716 (November 1979), page 648, ibid. 307105 (November 1989), pages 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemie et Phisique Photographe, Paul Montel, 1967), "Photoemulsion Chemistry". Published by Focal Press (GF Duffin, Photographic Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions" by Zelikman et al., VL Zelikman, et al., (Making and Coating Photographic Emulsion, Focal Press, 1964) and the like. .

  Monodispersed emulsions described in US Pat. Nos. 3,574,628, 3,655,394, and British Patent 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); U.S. Pat. No. 4,434,226, 4 No. 4,414,310, No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157.

  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. Also, a mixture of various crystal grains may be used.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell 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. The additive used in such a process is RDNo. 17643, ibid. 18716 and the same No. 307105, and the corresponding parts are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The coating amount of silver in film for a silver halide color photographic light-sensitive material of the present invention is preferably 6.0 g / m ² or less, more preferably 4.5 g / m ² or less, 2.0 g / m ² or less and most preferably . The applied silver amount is 0.01 g / m ² or more, preferably 0.02 g / m ² or more, more preferably 0.5 g / m ² or more.

In any one of the photographic constituent layers composed of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer (intermediate layer, protective layer, etc.) provided on the support, preferably a silver halide emulsion layer The 1-aryl-5-mercaptotetrazole compound is preferably added in an amount of 1.0 × 10 ^{−5 to} 5.0 × 10 ⁻² mol, and more preferably 1.0 × 10 ⁻⁴ to 1 per mol of silver halide. It is preferable to add 0.0 × 10 ⁻² mol. By adding in this range, the stain on the processed color photographic surface after the continuous processing can be further reduced.

As such a 1-aryl-5-mercaptotetrazole compound, an aryl group at the 1-position is preferably an unsubstituted or substituted phenyl group, and preferred specific examples of this substituent include acylamino groups (for example, acetylamino, -NHCOC ₅ H ₁₁ (n) etc.), ureido group (eg methylureido etc.), alkoxy group (eg methoxy etc.), carboxylic acid group, amino group, sulfamoyl group etc. A plurality (2 to 3 etc.) may be bonded. Further, the position of the substituent is preferably the meta or para position. Specific examples thereof include 1- (m-methylureidophenyl) -5-mercaptotetrazole and 1- (m-acetylaminophenyl) -5-mercaptotetrazole.

  The photographic additives that can be used or used in the present invention are described in the following Research Disclosure Journal (RD), and the description locations related to the following table are shown.

Various dye-forming couplers can be used in the silver halide color photographic light-sensitive material of the present invention, and the following dye-forming couplers are particularly preferred.
Yellow coupler: coupler represented by general formulas (I) and (II) of European Patent EP502,424A; coupler represented by general formulas (1) and (2) of European Patent EP513,496A (Especially Y-28 on page 18); couplers represented by general formula (I) of claim 1 of JP-A-5-307248; 45-1 of column 1 of US Pat. No. 5,066,576 Coupler represented by general formula (I) on line 55; coupler represented by general formula (I) in paragraph 0008 of JP-A-4-274425; claim 40 on page 40 of EP 498,381A1 (Especially D-35 on page 18); couplers represented by general formula (Y) on page 4 of European Patent EP447,969A1 (especially Y-1 (page 17), Y-54 ( 41)); United States The couplers represented by the formulas (II) to (IV) in columns 7 to 58 of column 7 of the specification No. 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19) )).

Magenta coupler: JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13)); European Patent EP 456,257 A-4-63 (page 134), A-4-73, -75 (page 139); European Patent EP 486,965, M-4, -6 (page 26), M-7 (page 27). ); M-45 in paragraph 0024 of JP-A-6-43611, M-1 in paragraph 0036 in JP-A-5-204106; M-22 in paragraph 0237 of JP-A-4-362631.
Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14 to 16) of JP-A-4-204843; C-7,10 (35 of JP-A-4-43345) Pages), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); and general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385 Coupler represented by Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.

  Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, German Patent GB 2,125570, European Patent EP 96,873B, German Patent DE 3,234,533. Those described in the document are preferred. A coupler for correcting unwanted absorption of the coloring dye is yellow represented by the general formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1. Colored Cyan Coupler (especially YC-86 on page 84), Yellow Colored Magenta Coupler ExM-7 (page 202, EX-1 (page 249), EX-7 (page 251), US Patent) described in the European Patent Specification No. 4,833,069, magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10), US 4,837,136 (2) (column 8), International Publication WO92 / A colorless masking coupler represented by the general formula [C-1] of claim 1 of No. 11575 (particularly, exemplified compounds on pages 36 to 45) is preferable.

Examples of compounds (including dye-forming couplers) that react with oxidized developing agents to release photographically useful compound residues include the following.
Development inhibitor releasing compound: a compound represented by any one of the general formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (particularly T-101) (Page 30), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), European Patent EP 436, The compound represented by the general formula (I) described on page 7 of the specification of 938A2 (particularly D-49 (page 51)), the compound represented by the general formula (1) of JP-A-5-307248 ( In particular, the compound represented by any one of the general formulas (I), (II) and (III) described in paragraph (0027) (23)) and pages 5 to 6 of European Patent EP440,195A2 (particularly page 29) I- (1));
Bleach accelerator releasing compounds: compounds represented by general formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (61) on page 61) and JP-A-6 Compound represented by formula (I) of claim 1 of JP-A-59411 (particularly paragraph (0022) (7));
Ligand-releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly the compound in columns 21 to 41 of column 12);
Leuco dye releasing compounds; compounds 1-6 of columns 3-8 of US Pat. No. 4,749,641;
Fluorescent dye-releasing compound: a compound represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (particularly compounds 1 to 11 in columns 7 to 10);
Development accelerator or fogging agent releasing compound: compound represented by general formula (1), (2), (3) in column 3 of U.S. Pat. No. 4,656,123 (especially (I- 22)) and ExZK-2 on page 75, lines 36-38 of EP 450,637A2;
Compound that releases a group that becomes a dye only after leaving: Compound represented by general formula (I) of claim 1 of US Pat. No. 4,857,447 (particularly, Y-1 to Y-19 in columns 25 to 36) .

As additives other than the dye-forming coupler, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140) of JP-A-62-215272 ˜144);
Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363;
Oxidizing agent scavenger for developing agent: Compound (especially I- (1), (2), (6) in column 2, lines 54 to 62 of U.S. Pat. No. 4,978,606. ), (12) (columns 4-5)), U.S. Pat. No. 4,923,787, column 2, line 5-10, in particular compound 1 (column 3);
Stain inhibitor: General formulas (I) to (III) on page 4, lines 30 to 33 of EP 298321A, in particular I-47, 72, III-1, 27 (pages 24 to 48);
Antifading agent: A-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (69 of EP 298321A) -118), U.S. Pat.No. 5,122,444, columns 25-38, II-1 to III-23, especially III-10, and EP 471347A, pages 8-12, I-1. ~ III-4, in particular II-2, U.S. Pat. No. 5,139,931, columns 32-40, A-1 to 48, in particular A-39,42;
Materials that reduce the amount of color-enhancing agent or color mixing inhibitor used: I-1 to II-15, especially I-46, pages 5 to 24 of EP 4131324A;
Formalin scavenger: European patent EP 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-A-1-214845, general formula (VII) to columns 13-23 of U.S. Pat. No. 4,618,573 Compound (H-1 to 54) represented by (XII), Compound (H-1 to 76) represented by formula (6) at the lower right of page 8 of JP-A-2-214852, particularly H-14 A compound according to claim 1 of US Pat. No. 3,325,287;
Development inhibitor precursor: compounds described in claim 1 of P-24, 37, 39 (pages 6-7) of JP-A-62-168139, US Pat. No. 5,019,492, particularly column 7 28-29;
Preservatives, antifungal agents: U.S. Pat. No. 4,923,790, columns 3-15, I-1 to III-43, in particular II-1,9,10,18, III-25;
Stabilizer, antifoggant: US Pat. No. 4,923,793, columns 6-16, I-1 to (14), in particular I-1,60, (2), (13), US Pat. Compounds 1 to 65, in particular 36, in columns 25 to 32 of 4,952,483;
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324;
Dye: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially a-1, 12, 18, 27, 35, 36, b-5, pages V to 27 to 29 -23, in particular V-1, F-I-1 to F-II-43, in particular F-I-11, F-II-8, European patent EP 457153A, pages 33 to 55 of EP 445627A. Pp. 17-28, III-1 to 36, especially III-1,3, European Patent EP 319999A, pages 6 to 11, Compounds 1 to 22, particularly Compound 1, European Patent EP 519306A Compounds D-1 to 87 represented by (1) to (3) (pages 3 to 28), Compounds 1 to 22 represented by general formula (I) in U.S. Pat. No. 4,268,622 Columns 3-10), U.S. Pat. No. 4,923,788. A compound represented by the general formula (I) (1) ~ (31) (columns 2-9);
UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by general formula (1) in JP-A No. 46-3335, and general formulas of European Patent EP520938A Compounds (3) to (66) (pages 10 to 44) represented by (I) and compounds HBT-1 to HBT-10 (page 14) represented by general formula (III), European Patent EP521823 Compounds (1) to (31) represented by general formula (1): (columns 2 to 9).

  In the present invention, non-bleachable colored materials are preferably used in combination. The non-bleachable colored material does not come out of bath or lose color during development processing, and the light absorption characteristics in the film before and after the processing are practically unchanged. There is no restriction | limiting in particular about the kind, Various dyes and pigments containing a well-known substance can be used.

  Known dyes include, for example, oxonol dyes, azomethine dyes, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, arylidene dyes, styryl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, azine dyes, oxazines And dyes, thiazine dyes, perinone dyes, merocyanine dyes, cyanine dyes, indoaniline dyes, phthalocyanine dyes, indigo dyes, and thioindigo dyes.

  As for known pigments, for example, azo pigments (insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments), phthalocyanine pigments, dyed lake pigments (acidic dye lakes, basic dye lakes), condensed Organics such as polycyclic pigments (quinacridone pigments, thioindigo pigments, perylene pigments, anthraquinone pigments, perinone pigments, dioxazine pigments, isoindolinone pigments, diketopyrrolopyrrole pigments) and others (nitroso pigments, alizarin lake pigments, alkali blue) Mention may be made of pigments.

  For specific compounds, please refer to “New Edition Dye Handbook” (Organic Synthetic Chemistry Association; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Color Material Engineering Handbook” (Color Material Association Edition; Asakura Shoten) 1989), “Revised New Handbook of Pigments” and the like. As specific examples of preferred dyes and pigments, D-1 to D-35 and P-1 to P-30 described in paragraph No. 0191 to paragraph No. 0250 of JP-A No. 11-95371 can be preferably exemplified. In addition, the method for adding these to the light-sensitive material is also described in detail in paragraph Nos. 0206 to 0215 of the patent, and these described parts are incorporated as part of the specification of the present application.

In the present invention, among the above, preferably better dye than the pigment, although the amount used 1 to 100 mg / m ² is generally preferably 5 to 100 mg / m ^2, more preferably 10 to 50 mg / m ² .

  Below, the compound represented by general formula (FS) used for this invention is demonstrated in detail.

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

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

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

  c and d each independently represents an integer of 4 to 8. As long as c and d are integers of 4 to 8, they may be different or the same. c and d are preferably integers of 4 to 6 and a = b, more preferably 4 or 6 and a = b, and more preferably a = b = 4. .

x represents 0 or 1, both of which are likewise preferred.
M represents a cation, and as the cation represented by M, for example, alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions and the like are preferable. Applied. Of these, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

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

  In general formula (FS-a), a, b, c, d, M, and x have the same meanings as those in general formula (FS), and preferred ranges thereof are also the same.

  Among the general formula (FS), the following general formula (FS-b) is more preferable.

  In general formula (FS-b), a1 represents the integer of 2-3. c1 represents an integer of 4 to 6. M represents a cation. x represents 0 or 1;

  2 is preferable as a1. c1 is preferably 4. x is preferably 0 or 1.

  Although the specific example of the preferable surfactant used for this invention is illustrated below, this invention is not limited to these specific examples.

  In the present invention, when the surfactant is used in the layer of the photographic material, the aqueous coating composition containing the surfactant may be composed of only the surfactant used in the present invention and water, depending on the purpose. And may contain other components as appropriate.

  In the above aqueous coating composition, two kinds of surfactants used in the present invention may be used according to the combination defined in the present invention, or three or more kinds may be mixed and used. Moreover, you may use another surfactant within the structure prescribed | regulated to this invention with the surfactant used for this invention. Examples of the surfactant that can be used in combination include various anionic, cationic, and nonionic surfactants, and may be a polymeric surfactant. Of these, anionic or nonionic active agents are more preferred. Examples of surfactants that can be used in combination include, for example, JP-A-62-215272 (pages 649 to 706), Research Disclosure (RD) Item 17643, pages 26 to 27 (December 1978), 18716,650. Page (November 1979), 307105, pages 875-876 (November 1989), and the like.

  A representative compound that may be contained in the aqueous coating composition is a polymer compound. The polymer compound may be a polymer soluble in an aqueous medium or an aqueous dispersion of a polymer (so-called polymer latex). The soluble polymer is not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the polymer latex includes various vinyl monomers (for example, acrylates). Derivatives, methacrylate derivatives, acrylamide derivatives, methacrylamide derivatives, styrene derivatives, conjugated diene derivatives, N-vinyl compounds, O-vinyl compounds, vinyl nitriles, other vinyl compounds (for example, ethylene, vinylidene chloride)) homopolymers or copolymers And a dispersion of a condensation polymer (for example, polyester, polyurethane, polycarbonate, polyamide). Detailed examples of this type of polymer compound are disclosed in, for example, JP-A-62-215272 (pages 707 to 763), Research Disclosure (RD) Item 17643, 651 (December 1978), page 18716, 650 ( 1979), 307105, 873-874 (November 1989), and the like.

  The medium in the aqueous coating composition may be water alone, or an organic solvent other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, etc.) and water. A mixed solvent may be used. The ratio of water in the aqueous coating medium is preferably 50% by mass or more.

  The aqueous coating composition may contain various compounds depending on the layer of the photographic photosensitive material to be used, and they may be dissolved in a medium or dispersed. Examples thereof include various couplers, ultraviolet absorbers, color mixing inhibitors, antistatic agents, scavengers, antifoggants, hardeners, dyes, and antifungal agents. In order to obtain effective antistatic ability and coating uniformity when used in a photographic light-sensitive material, it is preferably used for the uppermost hydrophilic colloid layer.

  In this case, in the coating composition of the layer, in addition to the hydrophilic colloid (for example, gelatin) and the fluorosurfactant used in the present invention, other surfactants, matting agents, slip agents, colloidal silica, gelatin A plasticizer or the like can be contained.

  There is no particular restriction on the amount of the surfactant represented by the general formula (FS), (FS-a) or (FS-b), and it is included in the structure of the surfactant, its use, and the aqueous composition. The amount used can be arbitrarily changed depending on the kind and amount of the compound to be prepared, the composition of the medium, and the like. For example, when the surfactant used in the present invention is used as a coating liquid for the uppermost hydrophilic colloid (gelatin) layer of a photographic photosensitive material which is a preferred embodiment of the present invention, the concentration (% by mass) in the coating solution is 0.003 to 2.0%, and preferably 0.03 to 10% based on the gelatin solid content.

In the silver halide color photographic light-sensitive material of the present invention, the total hydrophilic colloid layer on the side having the emulsion layer preferably has a total film thickness of 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, 16 μm or less is particularly preferable. The total film thickness is 0.1 μm or more, preferably 1 μm or more, and more preferably 5 μm or more. Further, the film swelling speed T _1/2 is preferably 60 seconds or less, and more preferably 30 seconds or less. T _1/2 is defined as the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed for 3 minutes at 35 ° C. with a color developer is defined as the saturated film thickness. To do. 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), Vol. 19, 2, pp. 124-129 can be used for measurement. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.

  Further, the swelling rate is preferably 180 to 280%, and more preferably 200 to 250%. Here, the swelling ratio is a scale representing an equilibrium swelling amount when the silver halide photographic light-sensitive material of the present invention is immersed in distilled water at 27 ° C. and swollen, and the swelling ratio (unit:%) = when swollen Total film thickness / total film thickness during drying × 100. The swelling ratio can be adjusted to the above range by adjusting the amount of gelatin hardener added.

The silver halide color photographic light-sensitive material for movies of the present invention can be processed by the standard processing steps for film positive light-sensitive materials.
Standard processing (excluding drying) for conventional film positive photosensitive materials
(1) Color developing bath (2) Stop bath (3) Washing bath (4) First fixing bath (5) Washing bath (6) Bleaching acceleration bath (7) Bleaching bath (8) Washing bath (9) Sound development (Paint development)
(10) Washing with water (11) Second fixing bath (12) Washing bath (13) Stabilization bath

  In the present invention, among the above processing steps, the color development time (step (1) above) is 2 minutes 30 seconds or less (lower limit is preferably 6 seconds or more, more preferably 10 seconds or more, further preferably 20 seconds). Above, most preferably 30 seconds or more), more preferably 2 minutes or less (lower limit is the same as 2 minutes 30 seconds), a preferable result can be obtained.

Hereinafter, the support will be described.
In the present invention, a transparent support is preferable, and a plastic film support is more preferable. Examples of the plastic film support include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, polystyrene, and polyethylene.

  Among these, a polyethylene terephthalate film is preferable, and a biaxially stretched and heat-set polyethylene terephthalate film is particularly preferable from the viewpoint of stability and toughness.

  Although there is no restriction | limiting in particular as thickness of the said support body, 15-500 micrometers is common, especially 40-200 micrometers is preferable from points, such as a handleability and versatility, and 85-150 micrometers is the most preferable. The transmissive support preferably means a substrate that transmits 90% or more of visible light, and contains dyed silicon, alumina sol, chromium salt, zirconium salt, etc. as long as it does not substantially interfere with light transmission. It may be.

  In order to firmly adhere the photosensitive layer to the surface of the plastic film support, the following surface treatment is generally performed. The same surface treatment is generally performed on the surface on which the antistatic layer (back layer) is formed. (1) Directly after surface activation treatment such as 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, ozone oxygen treatment, etc. There are two methods: a method in which a photographic emulsion (photosensitive layer forming coating solution) is applied to obtain an adhesive force; There is a law.

  Of these, the method (2) is more effective and widely used. In any of these surface treatments, a slightly polar group is formed on the surface of the support that was originally hydrophobic, a thin layer that is a negative factor for surface adhesion is removed, It seems to increase the crosslink density and increase the adhesive strength. As a result, the affinity with the polar group of the component contained in the undercoat layer solution increases and the fastness of the adhesive surface increases. It is considered that the adhesion between the undercoat layer and the support surface is improved.

  A non-photosensitive layer containing conductive metal oxide particles is preferably provided on the surface of the plastic film support on which the photosensitive layer is not provided. As the binder for the non-photosensitive layer, acrylic resin, vinyl resin, polyurethane resin and polyester resin are preferably used. This non-photosensitive layer is preferably hardened, and as the hardener, aziridines, triazines, vinyl sulfones, aldehydes, cyanoacrylates, peptides, epoxies, melamines, etc. are used. However, from the viewpoint of firmly fixing the conductive metal oxide particles, melamine compounds are particularly preferable.

The material of the conductive metal oxide particles includes ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ and V ₂ O _5, and complex oxides thereof, and these Examples of the metal oxide further include metal oxides containing different atoms.

As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , MgO, and V ₂ O ₅ are preferable, and SnO ₂ , ZnO, In ₂ O ₃ , TiO _2, and V ₂ are further preferable. O ₅ is preferred, and SnO ₂ and V ₂ O ₅ are particularly preferred. Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₂ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. If the amount of the different element added is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. If it exceeds 30 mol%, the degree of blackening of the particles increases, and charging Since the prevention layer is darkened, it is not suitable for a photosensitive material. Accordingly, the material of the conductive metal oxide particles is preferably a material containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

  The conductive metal oxide particles should have a volume ratio of 50% or less with respect to the entire non-photosensitive layer, but preferably 3 to 30%. The coating amount is preferably in accordance with the conditions described in JP-A-10-62905. When the volume ratio exceeds 50%, dirt is likely to adhere to the surface of the processed color photograph. When the volume ratio is less than 3%, the antistatic ability does not function sufficiently.

  The particle diameter of the conductive metal oxide particles is preferably as small as possible in order to reduce light scattering as much as possible, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter, and Mie's theory Can be obtained using In general, the average particle size is 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm. Here, the average particle size is a value including not only the primary particle size of the conductive metal oxide particles but also the particle size of the higher order structure.

  When the metal oxide fine particles are added to the coating solution for forming the antistatic layer, they may be added and dispersed as they are, but they are dispersed in a solvent such as water (including a dispersant and a binder as necessary). It is preferably added in the form of a dispersion.

  The non-photosensitive layer preferably contains a cured product of the binder and the hardener as a binder for dispersing and supporting the conductive metal oxide particles. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use water-soluble binders and hardeners, or use them in an aqueous dispersion state such as an emulsion. Moreover, it is preferable that a binder has any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with a hardening agent is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of the hydroxyl group or carboxyl group in the binder is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

  Hereinafter, the resin preferably used as the binder will be described. As acrylic resin, acrylic acid; acrylic acid esters such as alkyl acrylate; acrylamide; acrylonitrile; methacrylic acid; methacrylic acid esters such as alkyl methacrylate; homopolymer of any monomer of methacrylamide and methacrylonitrile Or a copolymer obtained by polymerization of two or more of these monomers. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers Is preferred. For example, a homopolymer of any one of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or a copolymer obtained by polymerization of two or more of these monomers. .

  The acrylic resin is mainly composed of a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with the hardener is possible with the above composition as a main component. It is preferable that the polymer is obtained in the above manner.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / A (meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer). preferable.

  The vinyl resin is polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl holmaral, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate so that a crosslinking reaction with a hardener is possible. The other polymer is a polymer obtained by partially using a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with the hardener.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the polyester resin, for example, after the reaction between the polyol and the polybasic acid is completed, the hydroxyl group and carboxyl group remaining unreacted can be used as functional groups capable of crosslinking reaction with the hardener. Of course, a third component having a functional group such as a hydroxyl group may be added. Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

  The melamine compound preferably used as a hardener includes a compound containing two or more (preferably three or more) methylol groups and / or alkoxymethyl groups in the melamine molecule and a melamine resin which is a condensation polymer thereof. Examples include melamine and urea resin. Examples of the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and the like, and specific commercial products thereof include, for example, SMITEX RESIN ( (Sumitex Resin) M-3, MW, MK, and MC (manufactured by Sumitomo Chemical Co., Ltd., all trade names), but are not limited thereto.

  Examples of the condensation polymer include hexamethylol melamine resin, trimethylol melamine resin, trimethylol trimethoxymethyl melamine resin, and the like. Commercially available products include MA-1 and MA-204 (Sumitomo Bakelite Co., Ltd., both trade names), Bekkamin MA-S, Bekkamin APM, and Bekkamin J-101 (Dainippon Ink Chemical Co., Ltd.). , All of which are trade names), Euroid 344 (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.), Oshika Resin M31 and Oshika Resin PWP-8 (product names of Oshika Promotion Co., Ltd., both trade names). However, it is not limited to these.

  As a melamine compound, it is preferable that the functional group equivalent shown by the value which divided the molecular weight by the number of functional groups in 1 molecule is 50-300. Here, the functional means a methylol group and / or an alkoxymethyl group. When this value exceeds 300, the curing density is small and high strength cannot be obtained, and when the amount of the melamine compound is increased, the coating property is lowered. If the curing density is small, scratches are likely to occur. Moreover, when the grade to harden | cure is low, the force holding an electroconductive metal oxide will also fall. If the functional group equivalent is less than 50, the curing density is increased, but the transparency is impaired, and even if the amount is reduced, it does not improve. The addition amount of the aqueous melamine compound is 0.1 to 100% by mass, preferably 10 to 90% by mass with respect to the polymer.

If necessary, the antistatic layer can be used in combination with a matting agent, a charge adjusting agent, a surfactant, a slipping agent and the like. As the matting agent, an oxide such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, more preferably 0.2 μm to 0.5 μm, a polymer such as polymethyl methacrylate and polystyrene, A copolymer etc. are mentioned. The preferred amount of matting agent is ^{2mg / m 2 ~15mg / m 2} .

  Examples of the charge control agent include surfactants described later, polymers containing fluorine atoms, inorganic salts, and organic salts. In particular, surfactants and polymers containing fluorine atoms, salts containing tetraalkylammonium ions, and the like are preferably used.

  Examples of the surfactant include arbitrary anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Examples of the slip agent include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

  The thickness of the antistatic layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior. A surface layer is preferably provided on the antistatic layer. The surface layer is provided mainly for improving the slipping property and scratch resistance and for assisting the detachment preventing function of the conductive metal oxide particles of the antistatic layer.

  Examples of the material for the surface layer include (1) wax, resin and rubber-like ones or copolymers of 1-olefinic unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Products (for example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and propylene / 1-butene copolymer), (2) A rubbery copolymer of two or more kinds of the 1-olefin and a conjugated or non-conjugated diene (for example, an ethylene / propylene / ethylidene norbornene copolymer, an ethylene / propylene / 1,5-hexadiene copolymer, and Isobutene / isoprene copolymer), (3) a copolymer of 1-olefin and conjugated or non-conjugated diene (for example, ethylene / Tadiene copolymers and ethylene / ethylidene norbornene copolymers), (4) 1-olefins, especially copolymers of ethylene and vinyl acetate and complete or partially saponified products thereof, and (5) 1-olefins alone or copolymerized. Examples thereof include, but are not limited to, a graft polymer obtained by grafting the above conjugated or non-conjugated diene or vinyl acetate onto a polymer, and a completely or partially saponified product thereof. The above compound is described in JP-B-5-41656.

  Among these, polyolefins having a carboxyl group and / or a carboxylate group are preferable. Usually used as an aqueous solution or aqueous dispersion.

  Water-soluble methylcellulose having a methyl group substitution degree of 2.5 or less may be added to the surface layer, and the addition amount is preferably 0.1 to 40% by mass with respect to the total binder forming the surface layer. The water-soluble methylcellulose is described in JP-A-1-210947.

  The surface layer may be formed on the antistatic layer by a well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, or extrusion coating. It can form by apply | coating the coating liquid (aqueous dispersion or aqueous solution) containing etc.

  The thickness of the surface layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior.

  The pH of the film in the silver halide color photographic light-sensitive material of the present invention is preferably 4.6 to 6.4, and more preferably 5.5 to 6.5. When the coating pH is higher than 6.5 in a long-time sample, the sensitization of the cyan image and the magenta image due to safelight irradiation is large. Conversely, when the coating pH is lower than 4.5, the photosensitive material is exposed. The yellow image density changes greatly with respect to the time change until development. Either case is a practical problem.

  The coating pH in the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic layers obtained by coating the coating solution on the support and does not necessarily match the pH of the coating solution. The coating pH can be measured by the following method as described in JP-A-61-245153. That is, (1) 0.05 ml of pure water is dropped on the surface of the photosensitive material coated with the silver halide emulsion. Next, (2) after standing for 3 minutes, the coating pH is measured with a surface pH measuring electrode (GS-165F, trade name, manufactured by Toa Denpa). The coating pH can be adjusted using an acid (for example, sulfuric acid or citric acid) or an alkali (for example, sodium hydroxide or potassium hydroxide) as necessary.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto.

Example 1
[Preparation of support]
Subjecting a primer on the emulsion paint設面side, an acrylic resin layer containing a side opposite to the below of the conductive polymer (0.05g / m ²⁾ and tin oxide fine particles (0.20g / m ²⁾ of emulsion paint設面the A coated polyethylene terephthalate film support (thickness: 120 μm) was prepared.

[Preparation of silver halide emulsion]
-Preparation of blue-sensitive silver halide emulsion-
Large emulsion (BO-01)
(Cube, particle size 0.65 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
It was prepared by adding a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 4 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.
Blue sensitizing dye (A ′); 3.5 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 2.2 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 1 .9 × 10 ⁻⁵ mol / mol silver Further, gold sulfur was sensitized optimally using chloroauric acid and triethylthiourea.

Medium size emulsion (BM-01)
(Cube, particle size 0.52 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
It was prepared by adding a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 6 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.
Blue sensitizing dye (A ′); 4.9 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 4.3 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 2 0.7 × 10 ⁻⁵ mol / mol silver Further, gold sulfur was sensitized optimally using chloroauric acid and triethylthiourea.

Small emulsion (BU-01)
(Cube, particle size 0.31 μm, particle size distribution 0.08, halogen composition Br / Cl = 3/97)
The preparation of BM-01 emulsion was the same as BM-01 except that the grain formation temperature was lowered.
Sensitizing dyes (A ′) to (C ′) represented by the structural formula described below were added as follows.
Blue sensitizing dye (A ′): 4.5 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (B ′): 4.1 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′): 7 .0x10 ^-5 mol / mol silver

-Preparation of red-sensitive silver halide emulsion-
Large size emulsion (RO-01)
(Cube, particle size 0.22 μm, particle size distribution 0.11, halogen composition Br / Cl = 5/95)
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 2 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (D ′) to (F ′) represented by the structural formula described later were added as follows and spectrally sensitized.
Red-sensitive sensitizing dye (D ′): 4.4 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 0.4 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.2 × 10 ⁻⁵ mol / mol silver Further, gold chloride is sensitized optimally using chloroauric acid and triethylthiourea, and then Cpd-71 represented by the structural formula described below is halogenated. 9.4 × 10 ⁻⁴ mol was added per 1 mol of silver.

Medium size emulsion (RM-01)
(Cube, particle size 0.17 μm, particle size distribution 0.12, halogen composition Br / Cl = 5/95)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.
Red-sensitive sensitizing dye (D ′): 7.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.4 × 10 ⁻⁵ mol / mol silver

Small emulsion (RU-01)
(Cube, particle size 0.12 μm, particle size distribution 0.13, halogen composition Br / Cl = 5/95)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.
Red-sensitive sensitizing dye (D ′): 8.9 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.2 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.5 × 10 ⁻⁵ mol / mol silver

-Preparation of green sensitive silver halide emulsion-
Large emulsion (GO-01)
(Cube, particle size 0.19 μm, particle size distribution 0.11, halogen composition Br / Cl = 3/97)
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. K ₂ [IrCl ₆ ] was prepared to be 2 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (G ′) to (J ′) represented by the structural formula described later were added as follows and spectrally sensitized.
Green sensitive sensitizing dye (G ′): 2.6 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 0.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.2 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver Further, using chloroauric acid and triethylthiourea, Gold sulfur sensitized.

Medium size emulsion (GM-01)
(Cube, particle size 0.14 μm, particle size distribution 0.13, halogen composition Br / Cl = 3/97)
Except having changed the particle formation temperature, it was carried out similarly to GO-01, and used the sensitizing dye (G ')-(J') represented by the structural formula mentioned later as follows.
Green sensitive sensitizing dye (G ′): 3.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.3 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.4 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver

Small emulsion (GU-01)
(Cube, particle size 0.094 μm, particle size distribution 0.19, halogen composition Br / Cl = 25/75)
Sensitizing dyes (G ′) to (J ′) represented by the structural formulas described later were used as follows except that the halogen composition and grain formation temperature were changed.
Green sensitive sensitizing dye (G ′): 5.1 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.7 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.9 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver

Small emulsion (GU-02)
(Cube, particle size 0.094 μm, particle size distribution 0.19, halogen composition Br / Cl = 3/93)
Emulsion GU-02 was prepared in the same manner as in the preparation of Emulsion GU-01, except that the halogen composition and the amounts of various compounds added were changed from GU-01.

Small emulsion (GU-03)
(Cube, particle size 0.13 μm, particle size distribution 0.13, halogen composition Br / Cl = 25/75)
In the preparation of emulsion GU-01, K ₂ [RhBr ₅ (H ₂ O)] was added at 5 × 10 ⁻⁸ mol / mole silver to the total silver amount, and the grain formation temperature and the amounts of various compounds were adjusted to GU-01. Emulsion GU-03 was prepared in the same manner except that the procedure was changed.

Small emulsion (GU-04)
(Cube, particle size 0.094 μm, particle size distribution 0.19, halogen composition Br / Cl = 25/75)
Emulsion GU-04 was prepared in the same manner as in the preparation of Emulsion GU-01 except that K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)] and the amounts of various compounds were changed from GU-01. Was prepared.

Small emulsion (GU-05)
(Cube, particle size 0.13 μm, particle size distribution 0.13, halogen composition Br / Cl = 25/75)
In the preparation of emulsion GU-01, K ₂ [RhBr ₅ (H ₂ O)] was added at 5 × 10 ⁻⁸ mol / mol silver to the total silver amount, and K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)], and emulsion GU-05 was prepared in the same manner except that the grain formation temperature and the amounts of various compounds were changed from GU-01.

Small emulsion (GU-06)
(Cube, particle size 0.13 μm, particle size distribution 0.13, halogen composition Br / Cl = 3/97)
In the preparation of emulsion GU-02, K ₂ [RhBr ₅ (H ₂ O)] was added at 5 × 10 ⁻⁸ mol / mol silver to the total silver amount, and the grain formation temperature and the amounts of various compounds were adjusted to GU-02. Emulsion GU-06 was prepared in the same manner except that the procedure was changed.

Small emulsion (GU-07)
(Cube, particle size 0.094 μm, particle size distribution 0.19, halogen composition Br / Cl = 3/97)
In the preparation of emulsion GU-02, emulsion GU- was similarly prepared except that K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)] and the amounts of various compounds were changed from GU-02. 07 was prepared.

Small emulsion (GU-08)
(Cube, particle size 0.13 μm, particle size distribution 0.13, halogen composition Br / Cl = 3/97)
In the preparation of emulsion GU-02, K ₂ [RhBr ₅ (H ₂ O)] was added at 5 × 10 ⁻⁸ mol / mol silver based on the total silver amount, and K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)], and emulsion GU-08 was prepared in the same manner except that the grain formation temperature and the amounts of various compounds were changed from GU-02.

Small emulsion (GU-09)
(Cube, particle size 0.13 μm, particle size distribution 0.13, halogen composition Br / Cl = 3/97)
In the preparation of emulsion GU-02, K ₂ [RhBr ₅ (H ₂ O)] was added at 5 × 10 ⁻⁸ mol / mol silver based on the total silver amount, and K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ ]. Emulsion GU-09 was prepared in the same manner except that the particle formation temperature and the amounts of various compounds were changed from GU-02.

[Preparation of dye solid fine particle dispersion]
The methanol wet cake of the compound (HD-1) was weighed so that the net amount of the compound was 240 g, 48 g of the following compound (Pm-1) was weighed as a dispersion aid, and water was added to make 4000 g. 'Flow-through sand grinder mill (UVM-2)' (manufactured by IMEX K.K.) is filled with 1.7 liters of zirconia beads (0.5 mm diameter), the discharge amount is 0.5 liter / min, and the peripheral speed is 10 m / s. For 2 hours. Thereafter, the dispersion was diluted so that the compound concentration was 3% by mass, and a compound (Pm-1) represented by the following structural formula was added by 3% by mass with respect to the dye (referred to as Dispersion A). The average particle size of this dispersion was 0.45 μm.
Further, a dispersion containing 5% by mass of the compound (HD-2) (referred to as Dispersion B) was obtained in the same manner.

[Preparation of Sample 101]
Each layer having the composition as shown below was coated on the support in a multilayer manner to prepare Sample 101 which was a multilayer color photographic light-sensitive material.

-Layer structure-
The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion coating amount represents a silver equivalent coating amount. Further, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.

[Layer structure of sample 101]
Support / polyethylene terephthalate film

First layer (antihalation layer (non-photosensitive hydrophilic colloid layer))
・ Gelatin 1.03
・ Dispersion A (as dye coating amount) 0.10
・ Dispersion B (as dye coating amount) 0.03

Second layer (blue sensitive silver halide emulsion layer)
A 3: 1: 6 mixture of silver chlorobromide emulsion BO-01, emulsion BM-01, and emulsion BU-01 (silver molar ratio). 0.57
Gelatin 2.71
-Yellow coupler (ExY ') 1.19
・ (Cpd-41) 0.0006
・ (Cpd-42) 0.01
・ (Cpd-43) 0.05
・ (Cpd-44) 0.003
・ (Cpd-45) 0.012
・ (Cpd-46) 0.001
・ (Cpd-54) 0.08
・ (Cpd-65) 0.02
・ Solvent (Solv-21) 0.26

Third layer (color mixing prevention layer)
・ Gelatin 0.59
・ (Cpd-49) 0.02
・ (Cpd-43) 0.05
・ (Cpd-53) 0.005
・ (Cpd-61) 0.02
・ (Cpd-62) 0.03
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

Fourth layer (red-sensitive silver halide emulsion layer)
A 2: 2: 6 mixture of silver chlorobromide emulsion RO-01, emulsion RM-01 and emulsion RU-01 (silver molar ratio) 0.40
Gelatin 2.79
・ Cyan coupler (ExC ') 0.80
・ (Cpd-47) 0.06
・ (Cpd-48) 0.06
・ (Cpd-50) 0.03
・ (Cpd-53) 0.03
・ (Cpd-57) 0.05
・ (Cpd-58) 0.01
・ (Cpd-60) 0.02
・ Solvent (Solv-21) 0.53
・ Solvent (Solv-22) 0.28
・ Solvent (Solv-23) 0.04

5th layer (color mixing prevention layer)
・ Gelatin 0.56
・ (Cpd-49) 0.02
・ (Cpd-43) 0.05
・ (Cpd-53) 0.005
・ (Cpd-62) 0.03
・ (Cpd-64) 0.002
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

Sixth layer (green sensitive silver halide emulsion layer)
-Silver chlorobromide emulsion GU-01 0.54
Gelatin 1.66
-Magenta coupler (ExM ') 0.73
・ (Cpd-49) 0.013
・ (Cpd-51) 0.001
・ Solvent (Solv-21) 0.15

7th layer (protective layer)
・ Gelatin 0.97
・ Acrylic resin (average particle size 2 μm) 0.002
・ (Cpd-55) 0.005
・ (Cpd-56) 0.08
・ (Cpd-59) 0.03
The compounds used here are shown below.

  Sample 101 was produced as described above.

<Preparation of Samples 102 to 109>
Next, Samples 102 to 109 were prepared in exactly the same manner as in the preparation of the photosensitive material 101 except that the emulsion GU-01 in the sixth layer was changed to GU-02 to GU-09, respectively.

<Preparation of Samples 111 to 119>
Furthermore, samples 111 to 119 of photosensitive materials differing only in that the surfactant (Cpd-55) in the seventh layer was replaced with (FS-1) in the photosensitive material 101 to 109 with an equal mass.

<Test and evaluation>
The samples 101 to 119 were subjected to the following evaluations in order to evaluate the stability of emulsion preparation, the stability against changes in temperature and humidity during exposure, and the stability of latent images.

-Evaluation of processing stability-
Emulsions GU-01 to GU-09 were each prepared 10 times, and samples 101 to 119 were prepared repeatedly. Using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K), gradation exposure for sensitometry at 1/100 second 60,000 lux through a gray filter that produces maximum density And processed according to the ECP-2 process published by Eastman Kodak Company. The density of the treated sample was measured with a green filter. For sensitivity display, the sensitivity is defined as the relative value of the logarithm of the reciprocal of the exposure amount necessary for the optical density to be increased by Dmin + 1.5. For magenta sensitivity, ΔG = (10 times average magenta sensitivity) − (minimum magenta sensitivity in 10 times) was used as a measure of processing stability. The lower each value, the more stable the emulsion preparation and the less processing variation, and the higher the processing stability.

-Stability evaluation against temperature and humidity changes during exposure-
Each sample was evaluated for the temperature and humidity environment during exposure as follows.
(1) 55 ° C relative humidity 55% (2) 25 ° C relative humidity 80%
For sensitometry using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K) through a gray filter that produces the maximum density with an exposure time of 1/100 seconds and an exposure illumination of 60,000 lux Of tone exposure. Processing was carried out according to the ECP-2 process published by Eastman Kodak Company. The density of the treated sample was measured with a green filter. In sensitivity display, the sensitivity is determined by taking a relative value of the logarithm of the reciprocal of the exposure amount necessary for the optical density to be increased by Dmin + 1.5. Find the magenta sensitivity for each sample,
SG1 = magenta sensitivity of (1) −magenta sensitivity of (2) was used as a measure of stability against changes in temperature and humidity during exposure.

-Latent image stability evaluation-
About the said samples 101-119, after preparation of a sample, after storing on the following conditions about each sample, the process shown below was implemented.
Gradation exposure for sensitometry was given, and after 30 minutes and 1 day after exposure, processing was carried out according to the ECP-2 process published by Eastman Kodak Company. The density of the treated sample was measured with a green filter. In sensitivity display, the relative value of the logarithm of the reciprocal of the exposure amount necessary to increase the optical density by Dmin + 1.5 was used as the sensitivity. Find the magenta sensitivity for each sample,
SG2 = magenta sensitivity at 30 minutes post-processing—magenta sensitivity at 1 day post-processing was used as a measure of latent image stability.

  Table 3 below shows the test results and evaluations regarding the processing stability, stability against changes in temperature and humidity during exposure, and latent image stability.

  From Table 3, it can be seen that samples 101, 102, 104, and 107 having small grain sizes of the present invention have poor emulsion preparation stability. Comparing Samples 116 and 118, it can be seen that the effect of the present invention is greater in the high silver chloride emulsion. Comparing Samples 108 and 109 with Samples 118 and 119, it can be seen that the sample containing the surfactant of the present invention is stable against changes in temperature and humidity during exposure and has high latent image stability.

(Example 2)
-Preparation of green sensitive silver halide emulsion-
Large emulsion (GO-02)
(Cube, particle size 0.35 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
Emulsion GO-02 was prepared in the same manner as in the preparation of Emulsion GO-01, except that the grain formation temperature and the amounts of various compounds were changed from GO-01.

Medium size emulsion (GM-02)
(Cube, particle size 0.26 μm, particle size distribution 0.11, halogen composition Br / Cl = 3/97)
Emulsion GM-02 was prepared in the same manner as in the preparation of Emulsion GM-01, except that the grain formation temperature and the amounts of various compounds were changed from GM-01.

Small emulsion (GU-10)
(Cube, particle size 0.23 μm, particle size distribution 0.10, halogen composition Br / Cl = 3/97)
Emulsion GU-10 was prepared in the same manner as in the preparation of Emulsion GU-02, except that the grain formation temperature and the amounts of various compounds were changed from GU-02.

Small emulsion (GU-11)
(Cube, particle size 0.23 μm, particle size distribution 0.10, halogen composition Br / Cl = 3/97)
Emulsion GU-08 was prepared in the same manner as in the preparation of Emulsion GU-08 except that the grain formation temperature and the amounts of various compounds were changed from GU-08.

Sample 201 was prepared by changing the configuration of the sixth layer in the production of the photosensitive material 111 as follows.
Sixth layer (green sensitive silver halide emulsion layer)
-1: 3: 6 mixture of silver chlorobromide emulsions GO-02, GM-02, and GU-10 (silver molar ratio) 0.54
Gelatin 1.66
-Magenta coupler (ExM ') 0.73
・ (Cpd-49) 0.013
・ (Cpd-51) 0.001
・ (Cpd-52) 0.02
・ (Cpd-55) 0.02
・ Solvent (Solv-21) 0.15

<Preparation of Samples 202 to 204>
Next, a sample 202 was prepared in exactly the same manner as in the preparation of the photosensitive material 201 except that the emulsion GU-10 in the sixth layer was changed to GU-11.
Next, Sample 202 was prepared in exactly the same manner as in the preparation of the photosensitive material 201 except that the emulsion GU-10 in the sixth layer was changed to GU-08.
Next, a sample 203 was prepared in the same manner as the photosensitive material 202 except that the emulsion GO-02 in the sixth layer was changed to GO-01 and GM-02 was changed to GM-01.

<Test and evaluation>
As in Example 1, the samples 201 to 203 were evaluated for stability against changes in temperature and humidity during exposure and stability of latent images.

-Graininess evaluation-
Using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K), each sample was exposed to 1/100 second through a green filter so that the density was Dmin + 1.0. Processing was performed according to the ECP-2 process published by Kodak. In order to evaluate the granularity of the green sensitive layer, RMS granularity was measured with a green filter using an aperture of 48 μmφ. The RMS value × 1000 of the density Dmin + 1.0 was defined as the RMS granularity, and the relative value of the RMS granularity of the sample 201 was evaluated. (Dmin represents the minimum image density) The smaller this value, the better the graininess. The average grain size in the table is the average grain size of all the mixed emulsions in the sixth layer.

Table 4 shows that the sample of the present invention is stable against changes in temperature and humidity during exposure and has high latent image stability. In addition, comparing the sample 202 with the samples 203 and 204, it is preferable that the average particle size is 0.25 μm or less because it is more stable against changes in temperature and humidity during exposure, has higher latent image stability, and has better graininess. I understand.

Claims (8)

A silver halide color photographic light-sensitive material for cinema having a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a transmission type support, wherein at least one of the silver halide emulsion layers contains silver chloride A silver halide emulsion having a ratio of 95 mol% or more, and the silver halide emulsion contains at least one metal complex represented by the following general formula (D1) and the following general formula (D2), and A silver halide color photographic light-sensitive material for cinema, comprising at least one compound represented by the following general formula (FS) in the silver halide color photographic light-sensitive material.
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
(In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, X ^D1 represents a halogen ion. L ^D1 is an arbitrary different from X ^D1 Wherein n represents 3, 4, 5 or 6, and m represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+, where A plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different, provided that the metal complex represented by the general formula (D1) is a ligand. (There is no or no CN ion.)
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
(In the general formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, L ^D2 represents an arbitrary ligand different from X ^D2, and n represents 3, 4, or 5) , M is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2 may be the same or different from each other, If L ^D2 is present, these may be the same or different.)

(In general formula (FS), A and B each independently represent a fluorine atom or a hydrogen atom. A and b each independently represent an integer of 1 to 6. c and d each independently. And represents an integer of 4 to 8. x represents 0 or 1. M represents a cation.) 2. The metal complex represented by the general formula (D1) is contained in silver halide grains in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol per mol of silver. Silver halide color photographic material for movies. 3. The movie halogenation according to claim 1, wherein the metal complex represented by the general formula (D1) is a metal complex represented by the following general formula (D1A). Silver color photographic light-sensitive material.
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
(In the general formula (D1A), M ^D1A represents Re, Ru, Os or Rh, X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os; ^{When D1A} is Rh, it represents H ₂ O, OH or O. n represents 3, 4, 5 or 6, m is the charge of the metal complex, and 4-, 3-, 2-, 1-, Represents 0 or 1+, wherein a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different. 4. The movie halogenation according to claim 1, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2A). Silver color photographic light-sensitive material.
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
(In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), L ^D2A represents an arbitrary inorganic ligand different from X ^D2A , n is 3, 4 or 5 and m is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2A may be the same or different from each other ^Or when there are a plurality of L ^{D2A s} , these may be the same or different.) The silver halide for cinema according to any one of claims 1 to 3, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2B). Color photographic material.
General formula (D2B)
[IrX ^D2B _n L ^D2B _(6-n) ] ^m
(In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or its base Represents a ligand in which a carbon or hydrogen atom in a part of the structure is replaced with another atom or atomic group, n represents 3, 4 or 5, m represents the charge of the metal complex, and 5-4 -, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2B may be the same or different from each other, and when a plurality of L ^D2B are present, they may be the same or different. .) 4. The movie halogenation according to claim 1, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2C). Silver color photographic light-sensitive material.
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
(In the general formula (D2C), X ^D2C represents a halogen ion or a pseudo-halogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand and contains at least one nitrogen atom in the ring skeleton. Represents a ligand containing at least one sulfur atom, and may have an optional substituent on a carbon atom in the ring skeleton, n represents 3, 4 or 5, and m represents the charge of the metal complex. 5-, 4-, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2Cs may be the same as or different from each other, and when a plurality of L ^D2Cs are present, May be the same or different.) 4. The movie halogenation according to claim 1, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2D). Silver color photographic light-sensitive material.
General formula (D2D)
[IrX ^D2D _n L ^D2D _(6-n) ] ^m
(In the general formula (D2D), X ^D2D represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2D is a 5-membered ring ligand and includes at least two nitrogen atoms in the ring skeleton. Represents a ligand containing at least one sulfur atom, and may have an optional substituent on a carbon atom in the ring skeleton, n represents 3, 4 or 5, and m represents the charge of the metal complex. 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2Ds may be the same as or different from each other, and when a plurality of L ^D2Ds are present, May be the same or different.) The silver halide color photographic light-sensitive material for movies according to any one of claims 1 to 7, wherein the silver sphere emulsion grains have an average equivalent sphere size of 0.25 µm or less.