JP2005121854A - Dye forming coupler and silver halide color photosensitive material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye forming coupler which reconciles a white background with color reproducibility of an image area in color development, and also to provide a silver halide color photosensitive material which is excellent in color reproducibility of a yellow simple color, color reproducibility of a magenta simple color and color reproducibility of red, and reproduces a white background very close to that of printing paper. <P>SOLUTION: The dye forming coupler is a compound represented by a formula (a) wherein R represents a substituent; Z represents a group of atoms required to form an N-containing 6- or 7-membered ring in combination with -N-C=N; R' represents a substituent; n represents an integer of 0-4; X represents H or a substituent; and A represents H or an atomic group which is released at the time of coupling with the oxidized product of a color developing agent and has specified spectral absorption in a visible light region. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel dye-forming coupler and a silver halide color light-sensitive material using the same, and more specifically, a dye-forming coupler excellent in yellow and magenta colors excellent in color reproducibility, and a color proof excellent in white background characteristics. The present invention relates to a silver halide color light-sensitive material.

  Silver halide color light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) are actively used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. For silver halide color photographic materials for general photography that have been widely used in the past, for example, in a method of photographing with a color negative film and printing a color image obtained through a development process using an optical system, the printing conditions are set in advance. With this setting, the printing conditions are easily determined and adjusted based on the result of measuring the density of the color negative film, and the color print photosensitive material (color photographic paper) is a full-color excellent color image with a single exposure. This is a system that can obtain print images continuously and has extremely high productivity.

  In addition, this color photographic paper has recently been used in a digital image forming method for forming a color image by modulating the amount of light from an exposure light source such as a laser or LED by image data taken with a digital camera or the like. . Also in digital image exposure, normally, modulated three-color lights of B, G, and R are mixed, and a color image is formed by one scan, which shows high productivity similar to the conventional one.

  In addition, recording materials using silver halide color light-sensitive materials are known to have low noise, particularly at low densities, and have characteristics that enable very smooth gradation reproduction. When the apparatus has a sufficient gradation reproduction capacity, it has a feature that it is excellent in highlight delineability. Because of these characteristics, silver halide color light-sensitive materials are widely used not only in the field of photography, but also in the field of printing, in the field of so-called color proofing for checking the state of finished prints in the middle of printing. It is becoming.

  In the field of proofing, a color image edited on a computer is output to a printing film, and the developed film is subjected to separation exposure while appropriately replacing the film, whereby yellow (Y), magenta (M), cyan (C ), And an image of the final printed matter is formed on color photographic paper, thereby determining the layout and color suitability of the final printed matter.

  Recently, a method of directly outputting an image edited on a computer to a printing plate has gradually become widespread, and in such a case, a color image can be obtained directly from the data on the computer without using a film. It was desired.

  For this purpose, various methods such as a sublimation type / melting heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image is expensive and inferior in productivity. In addition, there is a disadvantage that the image quality is inferior in a method that is low in cost and excellent in productivity.

  The system using silver halide color light-sensitive materials enables high-quality image formation, such as the ability to form accurate halftone images due to excellent sharpness, etc. On the other hand, continuous development processing is possible as described above. High productivity can be realized from the standpoints that images can be simultaneously written to a plurality of color image forming units.

  In recent years, digitization has progressed in the field of printing, and there is an increasing demand for obtaining an image directly from data in a computer. For the above-described reasons, for example, a halogen as disclosed in JP-A-2001-235816. Silver halide color light-sensitive materials are beginning to be used advantageously in this field.

  The most commonly used color image forming method in silver halide color light-sensitive materials is to react an oxidized aromatic primary amine color developing agent with a coupler using exposed silver halide as an oxidizing agent. To form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and similar dyes. In such a system, a method of reproducing a color image by a subtractive color method is used. In general, a color image is formed by changing the generation amounts of three colors of yellow, magenta, and cyan. Of these, acylacetanilide couplers are widely used as color developing couplers used for forming yellow dye images. A benzoyl acetanilide type compound having good color development is preferably used for a silver halide color photosensitive material for photographing, and a pivaloyl acetanilide type compound having an excellent color tone is preferably used for an ornamental silver halide color photosensitive material. The basic properties required for these couplers are not only to form a dye, but to have excellent spectral absorption characteristics of the formed dye, a high dye forming speed, a high color density, and It is desired to have various properties such as high fastness to light, heat and moisture of the formed dye. In particular, in recent years when high sensitivity and high image quality have been demanded for silver halide photographic light-sensitive materials, there is a strong demand for the development of couplers with high color density and high light-fastness of the dyes formed. .

  Examples of yellow couplers with improved color reproducibility, high color developability and light resistance include, for example, an alkoxy group at the 2-position of the anilide moiety as described in JP-A-63-123047, A yellow coupler having an acylamino group at the 5-position is exemplified. However, these couplers inherently have high pKa, and improvements are desired in terms of color development.

  In conventional yellow dye-forming couplers, the color reproducibility and extinction coefficient of the dyes formed are small, and a large amount of couplers and silver halides are required to obtain the required color density. There is a problem that the image quality is increased, the film thickness of the silver halide color photosensitive material is increased, and the sharpness of the obtained color image is lowered.

  Further, light resistance is not sufficient, and as a coupler for solving this problem, an acetanilide type coupler in which a pyrimidin-4-one in which an alkyl group having 1 to 6 carbon atoms is substituted with a nitrogen atom is bonded is disclosed (for example, , See Patent Document 1). As the leaving group of the coupler described in Patent Document 1, 1,2,3-triazole or 1,2,4-triazole is considered to be particularly preferable, but these couplers have been studied by the present inventors. In the silver halide color light-sensitive material using the above, it has been clarified that a white background portion where the coupler remains is preserved in a dark place, that is, a stain is generated.

  On the other hand, an acetanilide type coupler to which a pyrimidin-4-one substituted with a substituted alkyl group is bonded (for example, see Patent Document 2), and an acetanilide to which a pyrimidin-4-one substituted with an aryl group or a heterocyclic group is bonded. An acetanilide type coupler (for example, see Patent Document 4) to which a pyrimidin-4-one introduced with a divalent linking group such as a hetero atom is bonded. In addition, acetanilide type couplers (see, for example, Patent Document 5) to which pyrimidin-4-one substituted with an alkyl group having 7 or more carbon atoms are bonded have been proposed, and color reproducibility and light resistance are further improved. Yes.

  Further, for the purpose of further improving the color reproducibility of a yellow image, an acetanilide type coupler to which [1,2,4] thiadiazine-1,1-dioxide is bonded has been proposed (for example, Patent Documents 6 and 7). reference.).

  Further, as a magenta coupler, a pyrazolotriazole type magenta coupler having a specific substituent (see, for example, Patent Document 8), a pyrazolotriazole type magenta coupler having a large steric hindrance, a phosphate ester type, or a phosphine oxide type A method is disclosed in which magenta color reproducibility with high purity is obtained by combining with a compound (see, for example, Patent Document 9).

  On the other hand, in a silver halide color light-sensitive material, particularly a silver halide color light-sensitive material for reflection observation such as color photographic paper, the white background property is one of the important factors for increasing its commercial value. In particular, in color proofing, it is very preferable that the brightness, the hue, the surface quality, and the like not only approximate the printing paper, but also match. In particular, a white background obtained from a silver halide color light-sensitive material tends to have a yellow taste due to a coloring substance in a processing solution, and a fluorescent whitening agent can be used as a technique for apparently removing this yellow taste. Are known. However, it is not preferable to use a fluorescent brightening agent from the viewpoint of changing the effect depending on the type of light source to be observed and obtaining a stable white background.

  In addition, for the purpose of adjusting the hue of a white background with a yellowish taste, a technique for balancing the white background by adding a red or blue coloring compound remaining in the silver halide color photosensitive material after development processing is also widely known. ing. Recently, a technique has been proposed in which blue pigments such as indanthrone pigments, indigo pigments and indanthrone pigments, and red / purple pigments such as azo pigments, quinacridone pigments and dioxazine pigments are added to dispersed oil droplets such as couplers. (For example, refer to Patent Document 10).

  The couplers to which pyrimidin-4-one and the thiadiazine dioxide are bonded can obtain a dye image having a high purity in a single color, but are added for the purpose of adjusting a white background such as blue and red. The problem that the coloring compound caused unnecessary absorption in the long wavelength region of about 550 nm or more in the yellow spectrum as a result, and the purity as yellow was lowered. Further, even in a dye image obtained with a magenta coupler, there has also been a problem that the addition of a blue coloring compound causes unnecessary absorption to reduce the purity of magenta. Further, in the reproduction of red called so-called gold red, which is always pointed out in the closeness to the printed matter, the existence of unnecessary absorption of the bluish component has been a problem.

  In response to the above problems, color prints and color proofs containing colored couplers have been proposed (for example, see Patent Document 11). Patent Document 11 discloses a technique for improving the purity of a cyan dye image, particularly by using a magenta colored cyan coupler. However, a yellow coupler to which pyrimidin-4-one is bonded, and thiadiazin diene are disclosed. No mention has been made of yellow couplers to which oxides are bonded, and there is no suggestion about the compatibility between the color reproducibility and the white background in red dye images reproduced from magenta and yellow dyes. No.

In this way, the original color reproduction is achieved by a technique that satisfies the color reproducibility of a single color and is a problem common to silver halide color photosensitive materials using these couplers, and more closely approximates a white background on printing paper. Development of a silver halide color light-sensitive material that does not deteriorate has been demanded.
US Pat. No. 5,455,149 (Claims) JP 2002-296740 A (Claims) JP 2002-296671 A (Claims) JP 2002-318442 A (Claims) JP 2002-318443 A (Claims) JP 2002-351023 A (Claims) JP 2003-173007 A (Claims) JP 61-65245 A (Claims) JP-A-8-122984 (Claims) JP 2002-196457 A (Claims) JP-A-10-148920 (Claims)

  The present invention has been made in view of the above problems, and a first object thereof is to provide a dye-forming coupler that achieves both a white background during color development and color reproducibility of an image area. The second purpose is to provide a silver halide color photosensitive material that has excellent color reproducibility for yellow, magenta, and red, and that reproduces a white background that is very close to printing paper. It is to be.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
A dye-forming coupler, which is a compound represented by the following general formula (a):

[Wherein, R represents a substituent, and Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —N—C═N part. R 'represents a substituent, n represents an integer of 0 to 4, and X represents a hydrogen atom or a substituent. A represents an atomic group which is desorbed when coupled with a hydrogen atom or an oxidized form of a color developing agent and has a specific spectral absorption in the visible light region. ]
(Claim 2)
The Z in the general formula (a) is a residue forming a 3H-pyrimidin-4-one ring or a residue forming a 1H-pyrimidin-4-one ring. Dye-forming coupler.
(Claim 3)
Z in the general formula (a) is a residue forming a 2H- [1,2,4] thiadiazine-1,1-dioxide ring, or 4H- [1,2,4] thiadiazine-1,1-dioxide The dye-forming coupler according to claim 1, wherein the dye-forming coupler is a residue that forms a ring.
(Claim 4)
A dye-forming coupler, which is a compound represented by the following general formula (M1).

[Wherein, R ₁₁ and R ₁₂ each represent a substituent, and Y ₁ represents an atomic group which is eliminated when coupled with an oxidized form of a color developing agent and has a specific spectral absorption in the visible light region. ]
(Claim 5)
A dye-forming coupler, which is a compound represented by the following general formula (M2).

[Wherein, R ₂₁ and R ₂₂ each represent a substituent, and Y ₂ represents an atomic group which is eliminated when coupled with an oxidized form of a color developing agent and has a specific spectral absorption in the visible light region. ]
(Claim 6)
In the silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on the reflective support, the yellow image forming layer is A silver halide color photographic material comprising a dye-forming coupler represented by the formula (a).
(Claim 7)
In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the magenta image forming layer is A silver halide color light-sensitive material comprising a dye-forming coupler represented by the formula (M1).
(Claim 8)
In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the magenta image forming layer is A silver halide color light-sensitive material comprising a dye-forming coupler represented by the formula (M2).
(Claim 9)
In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the reflective support and the non-color-forming colloid 9. The silver halide color photosensitive material according to claim 6, wherein none of the layers contains a coloring substance remaining after color development.
(Claim 10)
In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the yellow image forming layer and the magenta image The silver halide color photosensitive material according to any one of claims 6 to 9, wherein the forming layer and the cyan image forming layer do not contain a pigment or an oil-soluble dye.

  According to the present invention, a dye-forming coupler that achieves color reproducibility of a white background and an image part at the time of color development, excellent color reproducibility of yellow single color, magenta single color, and red color reproducibility, and It is possible to provide a silver halide color light-sensitive material that reproduces a white background that is very close to printing paper.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

  First, the dye-forming coupler represented by the general formula (a) will be described.

  R in the general formula (a) represents a substituent, and the substituent represented by R is not particularly limited, but may be an alkyl group (for example, methyl group, isopropyl group, (t) butyl group, cyclohexyl group, dodecyl group). Group), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl etc.) Group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, tetrazolyl group, etc.), halogen atom (eg, chlorine atom, fluorine atom etc.), alkoxy group (eg, methoxy Group, propyloxy group, pentyloxy group, cyclohexyloxy group, etc.), aryloxy group (example) Phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group (eg, pyridyloxy group, tetrahydropyranyloxy group, etc.), alkoxycarbonyl group (eg, ethyloxycarbonyl group, octyloxycarbonyl group, etc.), aryloxy A carbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), a sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, cyclohexylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc.), Sulfamoyl group (for example, aminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, octylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc. Ureido groups (eg methylureido group, ethylureido group, cyclohexylureido group, octylureido group, phenylureido group, naphthylureido group etc.), acyl groups (eg acetyl group, propylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl) Group, 2-ethylhexylcarbonyl group, phenylcarbonyl group, pyridylcarbonyl group etc.), acyloxy group (eg acetyloxy group, ethylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group etc.), carbamoyl group (eg amino Carbonyl group, dimethylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), An acylamino group (eg, methylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, 2-ethylhexylcarbonylamino group, dodecylcarbonylamino group, naphthylcarbonylamino group, etc.), alkylsulfonyl group or arylsulfonyl group (eg, ethyl Sulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, 2-ethylhexylamino group, dodecyl) Amino group, anilino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group and the like. These groups are further substituted by the above substituents. It may be.

  The group represented by R is preferably an alkyl group or an aryl group, and more preferably an alkyl group having 2 to 24 carbon atoms in total, including a substituent further substituted on R, or similarly a total carbon number of 6 to 24 aryl groups. The group represented by R is more preferably an alkyl group having 2 to 18 carbon atoms in total including a substituent further substituted on R, or an aryl group having 6 to 18 carbon atoms in the same manner. Here, the group substituted for R may include a hetero atom, and the total number of carbon atoms does not include the number of hetero atoms.

  In the general formula (a), the group represented by R ′ represents a substituent, and n represents an integer of 0 to 4. n is preferably 0-2.

  There is no restriction | limiting in particular as a substituent represented by R ', The group synonymous with the group quoted by R in General formula (a) can be mentioned. R ′ is preferably an acylamino group, a sulfonylamino group, an oxycarbonyl group and the like.

  X represents a hydrogen atom or a substituent. Examples of the substituent represented by X include the same groups as the substituent represented by R ′. X is preferably an alkoxy group, an aryloxy group, a halogen atom, an amino group, an acylamino group, a ureido group or a sulfonamide group, more preferably an alkoxy group, an aryloxy group, a halogen atom or an acylamino group.

  Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —N—C═N part.

  Examples of the nitrogen-containing 6-membered ring formed by Z include pyrimidin-4-one, 1,3-diazine-4,6-dione, [1,3,5] triazin-2-one, [1,2, 4) Triazin-5-one, [1,2,4] thiadiazine-1,1-dioxide and the like.

  Examples of the nitrogen-containing 7-membered ring formed by Z include 1,3-diazepin-4-one, 1,3-diazepin-5-one, [1,2,4] thiadiazepine-1,1-dioxide, [ 1,3,5] thiadiazepine-1,1-dioxide and the like.

  Z is preferably a 6-membered ring, and preferably a 6-membered ring is a residue that forms a pyrimidin-4-one ring or a [1,2,4] thiadiazine-1,1-dioxide ring, more preferably Z is a residue that forms a 3H-pyrimidin-4-one ring, a residue that forms a 1H-pyrimidin-4-one ring, or 2H- [1,2,4] thiadiazine-1,1- It is a residue that forms a dioxide ring, or a residue that forms a 4H- [1,2,4] thiadiazine-1,1-dioxide ring.

That, Z is _{-C (-R 2) = C (} -R 3) -CO-, or _{-C (-R 2) = C (} -R 3) -SO 2 - represented by. R ₂ and R ₃ are bonded to each other to form a 5- to 7-membered ring together with the —C═C— moiety, or each independently represents a hydrogen atom or a substituent. The ring formed by combining R ₂ and R ₃ together with the —C═C— moiety is preferably a 5- to 7-membered alicyclic, aromatic, or heterocyclic ring, such as a benzene ring, a pyrazole ring, a furan A ring, a thiophene ring, a cyclopentene ring, and a cyclohexene ring. More preferably, the ring is a 6-membered aromatic ring, most preferably a benzene ring. When R ₂ and R ₃ represent a substituent, these may be the same or different, and examples of the substituent include those listed as examples of the substituent represented by the aforementioned R ′. .

  In the general formula (a), A represents an atomic group that is separated during coupling with an oxidized oxidant of the developing agent and has a specific spectral absorption in the visible light region.

  Examples of the atomic group represented by A in the general formula (a) include atomic groups such as anthraquinone, indigoid, azo, quinacridone, pyrrolopyrrole, dioxazine, pyrazolone, and naphthol. . The atomic group represented by A in the general formula (a) is preferably an anthraquinone-based, indigoid-based, or quinacridone-based atomic group.

  In the general formula (a), the group represented by A is an atomic group having a specific spectral absorption in the above-mentioned visible light region, but is a normal leaving group, that is, a hydrogen atom or an oxidized form of a developing agent. Some of them have a group that can be detached when coupled with. Examples of the group capable of leaving upon coupling with an oxidized form of the developing agent include, for example, phenoxy group, alkoxy group, acyloxy group, carbamoyl group, sulfonyl group, or nitrogen-containing heterocyclic group (for example, imidazolyl group, pyrazolyl group, or Hydantoinyl group, etc.). These groups represented by A can also have a substituent, and examples of the substituent include the same groups as those exemplified for the group represented by R in the general formula (a). More specifically, there can be mentioned those having the same meaning as the group represented by W described in paragraphs [0033] to [0043] of JP-A-8-29932.

  Specific examples of the dye-forming coupler (yellow coupler) represented by formula (a) according to the present invention are shown below, but the present invention is not limited thereto.

  The dye-forming coupler represented by the general formula (a) according to the present invention can be synthesized according to the method described in, for example, US Pat. No. 5,455,149, US Patent Publication No. 2003-64332, An example of synthesis is shown below.

  (Synthesis of Exemplified Compound 1)

  20 g of compound (A) was dissolved in 300 ml of methylene chloride, and 60 ml of methylene chloride solution in which 2.1 ml of bromine was dissolved was added dropwise under ice cooling. After stirring at room temperature for 45 minutes, water was added for liquid separation, and the organic layer was washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of compound (B). Subsequently, all of the crude product of compound (B) was dissolved in 185 ml of N, N-dimethylformamide, and 17.9 g of compound (C) and 38.0 ml of triethylamine were dissolved in N, N-dimethylform. The solution was added dropwise to a solution of formamide in 200 ml over 32 minutes. Thereafter, the mixture was stirred at room temperature for 1.5 hours, and ethyl acetate and water were added for liquid separation, and the organic layer was washed with 1 mol / L potassium carbonate aqueous solution, 1 mol / L hydrochloric acid aqueous solution and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 33.1 g of a crude product of compound (D). The total amount of the resulting crude product of compound (D) was dissolved in 150 ml of ethanol, and then 30 ml of water in which 5 g of sodium hydroxide was dissolved was added while stirring at room temperature. The solution was then heated to reflux for 1 hour. Thereafter, the solution was poured into 200 ml of water, and further 500 ml of ethyl acetate was added to separate the organic solvent phase. The separated organic phase solvent was removed under reduced pressure, and the resulting residue was dissolved in 65 ml of acetonitrile and recrystallized to obtain 25.9 g of a purified product of the exemplified compound (1). Identification was performed by 1H-NMR and mass spectrum.

  Next, the dye-forming coupler (magenta coupler) represented by the general formulas (M1) and (M2) of the present invention will be described.

The substituent represented by R ₁₁ in the general formula (M1) and the substituent represented by R ₂₁ in the general formula (M2) are the same as the substituent represented by R in the general formula (a). Can be mentioned. As the substituent represented by R ₁₁ in the general formula (M1) and the substituent represented by R ₂₁ in the general formula (M2), preferably an alkyl group, an alkynyl group, an alkenyl group, an aryl group, an alkoxy group, amino Group and the like, and an alkyl group is particularly preferable. Preferred examples of the alkyl group include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a neopentyl group, a pentyl group, a hexyl group, an octyl group, a t-octyl group, a dodecyl group, a cyclohexyl group, and an adamantyl group. It is done. R ₁₁ is particularly preferably a methyl group, an ethyl group, a pentyl group, or the like. These substituents may further have a substituent.

The substituent represented by R ₁₂ in the general formula (M1) and the substituent represented by R ₂₂ in the general formula (M2) are the same as the substituent represented by R in the general formula (a). Can be mentioned. The substituent represented by R ₁₂ in the general formula (M1) and the substituent represented by R ₂₂ in the general formula (M2) are preferably an alkyl group and an aryl group, and particularly preferably an alkyl group. The preferred alkyl group preferably has a substituent, and examples of the substituent include the same groups as those represented by R in formula (a). Examples of the substituent represented by R ₁₂ in the general formula (M1) and the substituent represented by R ₂₂ in the general formula (M2) include dye formation represented by the general formula (M1) or the general formula (M2). A coupler is preferably added to the silver halide color light-sensitive material and preferably has diffusion resistance so that it does not flow out into the processing solution when developed, and R ₁₁ in the compound represented by the general formula (M1). Or a substituent represented by R ₂₁ in the compound represented by the general formula (M2).

The group represented by Y ₁ in the general formula (M1) and the group represented by Y ₂ in the general formula (M2) are eliminated when coupled with the oxidized form of the color developing agent, and are specified in the visible light region. Represents an atomic group having the following spectral absorption. Eliminated when coupled with the oxidized group of the color developing agent represented by Y ₂ in the compound represented by formula (M2) and the group represented by Y ₁ in the compound represented by formula (M1). In addition, the atomic group having specific spectral absorption in the visible light region is not particularly limited as long as it has the function, and examples thereof include those having the same meaning as the group represented by A in the general formula (a).

  Specific examples of the dye-forming coupler represented by formula (M1) are shown below, but the present invention is not limited thereto.

  Next, specific examples of the dye-forming coupler represented by the general formula (M2) will be shown, but the present invention is not limited thereto.

  The dye-forming coupler represented by the general formula (M1) can be synthesized, for example, according to the method described in paragraphs [0049] to [0056] of JP-A-7-175186. Further, the dye-forming coupler represented by the general formula (M2) can be synthesized, for example, according to the method described in the claims of JP-A-5-186470.

Addition amount of the dye-forming coupler represented by general formula (a), general formula (M1), or general formula (M2) according to the present invention, that is, A in general formula (a), or Y ₁ in general formula (M1). The white background of the non-color-developing portion can be adjusted by adding the atomic group represented by Y ₂ in the general formula (M2). As the atomic group represented by A, a single group may be used, or a plurality of groups different depending on the structure may be used.

The dye-forming coupler represented by the general formula (a) is preferably used at an addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mmol per 1 m ² .

The yellow coupler used in the silver halide color light-sensitive material of the present invention is usually used in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide. be able to. The dye-forming coupler of the present invention can also be used in combination with other types of dye-forming couplers. For the yellow coupler used in the silver halide color light-sensitive material of the present invention, the methods and techniques used in ordinary dye-forming couplers are similarly applied.

In addition, the dye-forming coupler represented by the general formula (M1) or (M2) can adjust the white background of the non-color-developing portion by the addition amount thereof, that is, the addition amount of the atomic group represented by Y ₁ or Y _2. it can. As the atomic group represented by Y ₁ or Y ₂ , a single group may be used, or a plurality of groups different depending on the structure may be used.

The dye-forming coupler represented by the general formula (M1) or (M2) is preferably used at an addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mmol per 1 m ² .

The magenta coupler used in the silver halide color light-sensitive material of the present invention can be used in combination with other types of magenta couplers, and is usually 1 × 10 ⁻³ to 1 mol, preferably 1 × 10, per 1 mol of silver halide. It can be used in the range of ⁻² to 8 × 10 ⁻¹ mol.

  As the magenta coupler used in the silver halide color light-sensitive material of the present invention, as a magenta coupler that can be used together with the dye-forming coupler represented by the general formula (M1) or (M2) according to the present invention, for example, A compound represented by the general formula M-I or M-II described on page 2 of Kaihei 8-328210 is preferable. Specific examples of preferred compounds include MCP-1 to MCP-41 described on pages 6 to 16 of the same. Furthermore, other specific examples are described in compounds M-1 to M-61 described on pages 6 to 21 of European Patent Publication No. 273,712 and pages 36 to 92 of No. 235,913. Among the compounds 1 to 223 that are present are other than the representative examples described above.

In the silver halide color light-sensitive material of the present invention, the λ _max of the spectral absorption of the magenta image to be formed is preferably 530 to 560 nm, and λ L _0.2 is preferably 580 to 635 nm. λL _0.2 means a wavelength at which the absorbance is 0.2 longer than the wavelength indicating the maximum absorbance when the maximum absorbance is 1.0 in the spectral absorbance curve of the image dye. This amount is a reference amount indicating the magnitude of unnecessary absorption on the long wave side of the image dye, and indicates that the closer to λ _max is, the smaller unnecessary absorption is preferable.

  The magenta image forming layer of the silver halide color light-sensitive material of the present invention preferably contains a yellow coupler in addition to a magenta coupler. Preferred yellow couplers to be contained in the magenta image-forming layer of the silver halide color light-sensitive material of the present invention include known pivaloyl acetanilide type or benzoyl acetanilide type couplers. Specific examples of preferable yellow couplers to be contained in the magenta image forming layer of the silver halide color light-sensitive material of the present invention include, for example, YCP-1 to YCP-1-1 described on the right column on pages 6 to 15 of JP-A-8-314079. A coupler represented by YCP-39 is exemplified, but of course, the coupler is not limited thereto.

  In the silver halide color light-sensitive material of the present invention, a known phenol-based, naphthol-based, imidazole-based, or azole-based coupler can be used as the cyan coupler contained in the cyan image forming layer. For example, phenol couplers substituted with alkyl groups, acylamino groups, or ureido groups, naphthol couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol couplers introduced with an oxygen atom as a leaving group are representative. The Among these, preferred compounds include compounds represented by general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.

  As the azole coupler, a pyrazoloazole coupler represented by the general formula [I] or [II] described on page 2 of JP-A-8-171185, or described in JP-A-11-282138 Examples thereof include pyrroloazole couplers represented by the general formula (I).

The cyan coupler can be used usually in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide in the silver halide emulsion layer.

  In the silver halide color light-sensitive material of the present invention, a known yellow coupler, preferably an acylacetanilide-based coupler, etc. may be used together with the dye-forming coupler (yellow coupler) represented by the general formula (a) according to the present invention. it can.

  Specific examples of yellow couplers that can be used in combination include, for example, compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by Y-I-1 to Y-I-55, The compounds described on pages 11 to 14 of No. 209466 and compounds represented by Y-1 to Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described on page 21 of JP-A-6-95283, compounds of general formulas (I) and (II) described in JP-A-2002-352023, and the like can also be mentioned. .

In the silver halide color light-sensitive material of the present invention, the λ _max of the spectral absorption of the formed yellow image is preferably 425 nm or _more , and λL _0.2 is preferably 515 nm or less.

The spectral absorption λL _0.2 of the yellow color image is a value defined by the content described in JP-A-6-95283, page 21, right column, lines 1 to 24. It represents the magnitude of unnecessary absorption.

  In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, a compound having a known color tone adjusting action together with the compound represented by the general formula (HBS-1) according to the present invention Can be added. Examples of the compound for this purpose include a phosphate ester compound represented by the general formula [HBS-I] and a phosphine oxide compound represented by [HBS-II] described on page 22 of JP-A-6-95283. It is done.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in JP-A No. 64-90445, and a metal complex represented by the general formulas XII, XIII, XIV, XV described in JP-A No. 62-182741 are particularly preferable. Preferred for magenta dyes. Further, compounds represented by the general formula I ′ described in JP-A-1-196049 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  When using an oil-in-water emulsion dispersion method when adding an anti-stain agent or other organic compound used in the silver halide color light-sensitive material of the present invention, it is usually a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. In addition, if necessary, it is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling organic solvent after the dispersion or simultaneously with the dispersion may be incorporated. Examples of the high-boiling organic solvent that can be used for dissolving and dispersing the stain inhibitor include phosphate esters such as tricresyl phosphate and trioctyl phosphate, phosphine oxides such as trioctyl phosphine oxide, Higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A 4-265975 are preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  The silver halide emulsion used in the silver halide color light-sensitive material of the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride. Silver chloride, silver chlorobromide, silver chloroiodobromide, salt Those having an arbitrary halogen composition such as silver iodide are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. In a silver halide emulsion having a portion containing a high concentration of silver bromide, the portion containing a high concentration of silver bromide may be a so-called core-shell type silver halide emulsion, or a complete layer A so-called epitaxy-bonded region may be formed in which only regions having different compositions are present without being formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.

  The negative silver halide emulsion used in the silver halide color light-sensitive material of the present invention preferably contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent softening in the shadow region.

  Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole, etc. can be mentioned. Of these, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination with a plurality of ligands.

  The characteristics of these metal compounds can also be characterized as the depth of electron traps when incorporated in silver halide emulsion grains. Examples of the compound that gives a shallow electron trap having a depth of 0.2 eV or less include compounds having a second lead ion or a cyano ligand, which are effective in improving reciprocity failure, particularly low-illuminance failure. is there. In addition, examples of the compound that provides a deep electron trap having a depth of 0.35 eV or more include Ir, Rh, and Ru compounds having halide ions and nitrosyl ligands. These compounds can be preferably used for improving high intensity reciprocity failure. It is also preferable to use a compound that provides a shallow electron trap having a depth of 0.2 eV or less and a compound that provides a deep electron trap having a depth of 0.35 eV or more in combination. These compounds are described in detail in pages 4 to 5 of JP-A No. 2000-214561.

  As a method of containing heavy metal ions in the silver halide emulsion, the heavy metal compound is added to each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. What is necessary is just to add in arbitrary places.

The heavy metal compound can be dissolved together with the halide salt and added continuously throughout the grain formation process. It can also be prepared by forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The amount of heavy metal ions added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, particularly 1 × 10 ⁻⁸ mol or more, 5 mol or more per mol of silver halide. × 10 ⁻⁵ mol or less is preferable.

  Any silver halide grains can be used in the present invention. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.

  The grains used in the present invention are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions to the same image forming layer.

  The particle size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably in consideration of suitability for rapid processability and reaching sensitivity, and other photographic performance. Is in the range of 0.2 to 1.0 μm.

  This grain size can be determined by measuring the projected area of the silver halide grains or using an approximate diameter. If the silver halide grains are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.

  The grain size distribution of the silver halide grains used in the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0. .2 or more monodispersed emulsions of 15 or less are added to the same image forming layer. The variation coefficient here is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.

  As a silver halide emulsion preparation apparatus and preparation method, various methods known in the art can be used.

  The silver halide emulsion used in the present invention may be obtained by any of the acidic method, neutral method and ammonia method. The silver halide grains may be grown at a time, or may be grown after preparing seed grains. The method for preparing the seed particles and the method for growing them may be the same or different.

  Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, as one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A No. 54-48521 can be used.

  Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, the reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus for forming grains while keeping the distance between the silver halide grains constant by taking out and concentrating by ultrafiltration may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

  The negative silver halide emulsion used in the present invention can be appropriately combined with a sensitizing method using a gold compound, a sensitizing method using a chalcogen sensitizer, and the like. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The addition amount of the sulfur sensitizer is preferably appropriately changed depending on the type of silver halide emulsion to be applied and the expected effect, but is generally 5 × 10 ^{−10 to} 5 per mol of silver halide. The range is × 10 ⁻⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ per mole of silver halide. Mole is preferred. More preferably, it is 1 * 10 < ^-5 > -1 * 10 <^-8> mol. These compounds can also be added for various purposes not as a sensitizer but at the stage of preparing a coating solution.

  As a chemical sensitization method for the negative silver halide emulsion used in the present invention, a reduction sensitization method may be used.

  The silver halide color light-sensitive material of the present invention can also have a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.

  These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 g / ml.

As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A No. 58-105141 can be used. 8. A method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system under conditions of 60 to 80 ° C., and a surface tension described in JP-B-60-6496 of 3.8 × 10 ⁻² N / m or less A method of dispersing in the presence of a surfactant that suppresses to a low level, as disclosed in JP-A-50-80826, is dissolved in an acid that is substantially free of water and does not exceed pKa of 5, and is added to the aqueous liquid A method of dispersing and adding this dispersion to a silver halide emulsion can be used.

  The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.

  Examples of the dispersion apparatus that can be used to prepare the dispersion include, for example, a ball mill, a sand mill, an ultrasonic disperser, and the like, in addition to the high-speed stirring disperser described in FIG. 1 of JP-A-4-125561. Can be mentioned.

  Further, when using these dispersing devices, as described in JP-A-4-125632, a pre-treatment such as dry pulverization may be performed in advance, followed by wet dispersion.

  The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.

In the silver halide emulsion used in the present invention, for the purpose of preventing fogging that occurs during the preparation process of the silver halide color light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development, Known antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include nitrogen-containing heterocyclic mercapto compounds represented by the general formula (II) described in the lower column on page 7 of JP-A-2-14636. Specific examples of preferred compounds are (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP-A 2000- No. 267235, page 8, right column, lines 32 to 36, can be mentioned. Depending on the purpose, these compounds are added at any step such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, or a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 ×. 10 ⁻² mol is more preferred. When added to a layer other than the silver halide emulsion layer, the content in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  Other additives can be added to the silver halide emulsion used in the present invention for various purposes. For example, disulfides and polysulfide compounds such as A-20, C-1, C-9, C-14, C-15, C-16, C-40 and the like specifically described in JP-A-2-146036 It is preferable to use thiosulfonic acid compounds such as D-1, D-3, D-6 and D-8, inorganic sulfur and the like.

  In the silver halide color light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, page 308, and special dyes can be used. The dyes described in Kaihei 6-3770 are preferably used.

  The silver halide color light-sensitive material of the present invention preferably has at least one hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support in the silver halide emulsion layer. The hydrophilic colloid layer preferably does not contain a coloring substance remaining after color development.

In the silver halide color photographic material of the present invention, at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support in the silver halide emulsion layer is white. A pigment may be contained. For example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, and titanium dioxide is particularly preferable for various reasons. The white pigment is dispersed in a hydrophilic colloid aqueous solution binder such as gelatin so that the treatment liquid can penetrate. The coating amount of the white pigment is preferably in the range of 0.1 to 50 g / m ² , more preferably in the range of 0.2 to 5 g / m ² .

  Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, if necessary, an undercoat layer or a non-light-sensitive hydrophilic layer such as an intermediate layer at an arbitrary position. A colloid layer can be provided.

  Addition of a fluorescent brightening agent to the silver halide color light-sensitive material of the present invention is preferred in that the white background can be further improved. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye out of the silver halide color light-sensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  In the silver halide color light-sensitive material of the present invention, various known surfactants can be used in combination. As a preferable compound as a surfactant used for dispersing a photographic additive used in a light-sensitive material or adjusting the surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or its The thing containing a salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. A dispersion of an oil-soluble additive emulsified with these surfactants is usually added to a coating solution containing a silver halide emulsion. The time from application to application to application is preferably short, preferably within 10 hours, and more preferably within 3 hours and within 20 minutes.

  In the silver halide color light-sensitive material of the present invention, a compound which reacts with an oxidized developing agent is added to an intermediate layer provided between silver halide emulsion layers to prevent color turbidity. It is preferable to improve fog by adding it directly. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-133056, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17. .

  In the silver halide color photographic material of the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by III, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-1633, and compounds described in JP-A-5-165144 Examples include compounds represented by general formulas (I) and (II).

  In the silver halide color light-sensitive material of the present invention, it is advantageous to use gelatin as a binder. However, other gelatins such as gelatin derivatives, gelatin and other polymer graft polymers, and materials other than gelatin are used as necessary. Hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  As a hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. In order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the physical properties of the surface of the silver halide color light-sensitive material or the processed silver halide color light-sensitive material, for example, a slipping agent described in JP-A-6-118543 and JP-A-2-73250 is used as a protective layer. It is preferable to add a matting agent.

  As the support used for the silver halide color photosensitive material of the present invention, any material may be used, paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, Polypropylene which may contain a white pigment, polyethylene terephthalate support, baryta paper and the like can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the support having a water-resistant resin coating layer on the surface of paper, one having a thickness of 80 to 250 μm is usually used.

  In the support according to the present invention, it is preferable to use a support having a thickness of 80 to 150 μm. Such a base paper can be preferably used for a silver halide color light-sensitive material for digital color proof (DCP). In this case, the thickness of the support is preferably 90 to 140 μm in order to bring the feeling of handling closer to the printing paper. 100 to 130 μm is more preferable.

The characteristics of such a support can also be defined by mass, and usually a support having a mass of 50 to 300 g / m ² is used, but a support of approximately 80 to 150 g / m ² is preferable, and it is used for DCP. the support used in the silver halide color light-sensitive material is preferably 130 g / m ² or less of the support, the support of 70~120g / m ² is more preferable.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  In the present invention, it is preferable that the reflective support does not contain a coloring substance remaining after color development.

  The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved, which is preferable for forming a proof image.

  Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, more preferably 0.12 μm or less from the viewpoint of obtaining the effect of good glossiness.

  In the silver halide color light-sensitive material of the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and directly or undercoat layer (adhesiveness of the support surface, antistatic properties). , One or more subbing layers for improving dimensional stability, rub resistance, hardness, antihalation properties, friction properties and / or other properties).

  In applying the silver halide color light-sensitive material of the present invention, a thickener may be used for the purpose of improving the coating property. As the application method, extrusion coating or curtain coating capable of simultaneously applying two or more layers is particularly useful.

  Next, an image forming method using the silver halide color photographic material of the present invention will be described.

  As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).

  Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.

  The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of an LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, devices such as AOM and EOM (electro-optic modulator) are generally used.

  When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used as long as the amount of light is weak.

  Moreover, you may use an organic light emitting element as a light source which replaces these, These are described in Unexamined-Japanese-Patent No. 2000-258846 etc., for example.

  The emission wavelength of the light source can be preferably used in any wavelength region where the photosensitive material has sufficient sensitivity, but it has a sufficient sensitivity difference with other photosensitive layers in order to prevent color turbidity. It is preferable to use a region. Although it depends on the contrast of the photosensitive material, it is preferable that the common logarithm of the exposure amount has a sensitivity difference of 0.6 or more, preferably 1.0 or more. In addition, when the emission wavelength varies depending on the environmental conditions and operating conditions in which the light source is placed, it is theoretically preferable to match the peak wavelength of the spectral sensitivity. It is preferable to select the wavelength in consideration of the relationship. Examples thereof include JP-A-6-75342 and JP-A-2001-83663. Further, when not only the emission wavelength but also the emission intensity varies, it is preferable to select the emission wavelength in relation to the spectral sensitivity. Examples thereof include Japanese Patent Application Laid-Open No. 2002-72367 and Nikkei New Material September 1987. It is described on page 54 of the 14th of the month.

  In the present invention, the term area gradation image is used, but this is not expressed by the shading of the color of each pixel, but by the size of the area of the color developed at a specific density. It can be considered synonymous with halftone dots.

  Usually, in the case of area gradation exposure, the purpose can be achieved by causing Y, M, C, and black to be colored. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure using different exposure amounts of three or more values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In order to draw an image with such light, it is necessary to scan the silver halide color photosensitive material with a light beam. The silver halide color photosensitive material is wound around a cylindrical drum and rotated while rotating at high speed. A so-called cylindrical outer surface scanning method in which the light beam is moved in a direction perpendicular to the direction may be employed, and a so-called cylindrical inner surface scanning method in which a silver halide color photosensitive material is exposed in close contact with a cylindrical depression may be preferably used. A so-called plane scanning method may be employed in which the polyhedral mirror is rotated at a high speed, and the silver halide color photosensitive material conveyed thereby is exposed by moving the light beam perpendicular to the conveying direction. From the viewpoint of high image quality and obtaining a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide color photosensitive material must be brought into close contact with the cylindrical drum accurately. In order to reliably perform this close contact, it is necessary to accurately align and transport. The silver halide color light-sensitive material used in the present invention can be preferably used because the surface on the side to be exposed (the side on which the silver halide emulsion layer is coated) can be more accurately aligned. From the same viewpoint, the support used for the silver halide color photographic material used in the present invention has an appropriate rigidity, and a Taber rigidity of 0.8 to 4.0 is preferable.

  The diameter of the exposure drum can be arbitrarily set according to the size of the silver halide color photosensitive material to be exposed. The number of rotations of the exposure drum can be arbitrarily set, but an appropriate number of rotations can be selected depending on the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the silver halide color photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The silver halide color photosensitive material can be fixed to the exposure drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the silver halide color photosensitive material. In addition, the silver halide color light-sensitive material can be attracted and adhered. Adhering the silver halide color photosensitive material to the exposure drum as much as possible is important to prevent troubles such as image unevenness.

  As an apparatus used for image formation, a method in which a plurality of photosensitive materials are set in advance and the photosensitive materials are appropriately selected and used can be preferably used. In this case, the two types of photosensitive materials can be, for example, photosensitive materials having different widths or photosensitive materials having different surface properties (unevenness of the support). The selection of the photosensitive material may be a method of setting using a switch of the image forming apparatus or the like, or setting information may be transmitted together with image data and selected based on the setting information. It can also be advantageously used to automatically select the optimum size of the photosensitive material according to the size of the image data. In special cases, the same type of photosensitive material can be loaded, and when one photosensitive material is used up, the other photosensitive material can be automatically used. This is advantageous because continuous unattended operation is possible. Can be used.

  Next, the development process will be described.

  In the present invention, known compounds can be used as the aromatic primary amine developing agent used in the color development processing. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N , N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N Ethyl-N- (β-ethoxyethyl) aniline CD-11: 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the present invention, the color developer is in an arbitrary pH range. Although it can be used, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing.

  The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment is possible and the better. However, it is preferable that the temperature is not so high from the stability of the treatment liquid, and the treatment is more preferably performed at 37 ° C or higher and 60 ° C or lower.

  The color development time is generally about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds. In addition to the above color developing agent, a known developer component compound can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ions and benzotriazoles, a preservative and a chelating agent are used.

  The silver halide color light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be bleach-fixing performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative to a washing process.

  The development processing apparatus used for the development processing of the silver halide color photosensitive material of the present invention may be a roller transport type that transports the silver halide color photosensitive material sandwiched between rollers disposed in a processing tank, An endless belt system that fixes and transports the silver halide color photosensitive material may be used. However, the processing tank is formed in a slit shape, and the processing solution is supplied to the processing tank and the silver halide color photosensitive material is transported. A spray method in which the treatment liquid is sprayed, a web method by contact with a carrier impregnated with the treatment liquid, a method using a viscous treatment liquid, or the like can also be used. When processing a large amount of silver halide color light-sensitive material, it is usually performed using an automatic developing machine. In this case, it is preferable that the amount of replenisher to be replenished according to the processing amount is smaller. The most preferable treatment form in view of environmental suitability and the like is to add a treatment agent in the form of a tablet as a replenishment method, and as this method, the method described in published technical report No. 94-16935 is most preferred.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
<< Preparation of silver halide color photosensitive material >>
[Preparation of Sample 101]
A polyethylene laminated paper reflective support (Taber stiffness) with a mass per square meter of 115 g of laminated high-density polyethylene on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. = 3.5, PY value = 2.7 μm), each layer having the structure shown in Table 1 below was coated on the side of the polyethylene layer containing titanium oxide, and further on the back side, gelatin 6.00 g / Sample 101 which is a multilayer silver halide color photosensitive material coated with a layer containing m ² and a silica matting agent 0.65 g / m ² was prepared.

The coupler was dissolved in a high boiling point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. Moreover, (H-1) and (H-2) were added as a hardening agent. Moreover, (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >.

  As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

  The magenta couplers (M-1) and (M-2) used for the third layer are both couplers represented by the general formula (M2).

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- A mixture of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone in a mass ratio of 1: 1: 2. Q-4: 2,5-di -t- butyl hydroquinone PVP: Polyvinylpyrrolidone

  Each photosensitive silver halide emulsion used for the preparation of Sample 101 was prepared according to the following method.

(Preparation of blue-sensitive silver halide emulsion)
In 1 liter of 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were simultaneously added while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) And (Liquid D) were simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled according to the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or a sodium hydroxide aqueous solution.

<Liquid A>
Sodium chloride 3.42g
Potassium bromide 0.03g
Water added to finish 200ml <Liquid B>
Silver nitrate 10g
Water added to finish 200ml <C solution>
Sodium chloride 102.7g
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g
Water added to finish 600ml <Liquid D>
300 g of silver nitrate
Finished by adding water to 600 ml. After completion of addition, desalting was performed using a 5% aqueous solution of demole N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution to obtain an average particle size. A monodispersed cubic emulsion EMP-101 having 0.71 μm, a coefficient of variation of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

  The emulsion EMP-101 was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion Em-B101.

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX
Potassium bromide 0.2g / mol AgX
Next, in the preparation of the emulsion EMP-101, the average grain size was changed in the same manner except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-102 having a diameter of 0.64 μm, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

  A blue-sensitive silver halide emulsion Em-B102 was prepared in the same manner as in the preparation of the blue-sensitive silver halide emulsion Em-B101, except that the emulsion EMP-102 was used instead of the emulsion EMP-101. A blue-sensitive silver halide emulsion using a 1: 1 mixture of -B101 and Em-B102 in the seventh layer was prepared.

(Preparation of green sensitive silver halide emulsion)
In the preparation of the emulsion EMP-101, the average particle size of 0 was similarly obtained except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodisperse cubic emulsion EMP-103 having a thickness of .40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

  The emulsion EMP-102 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green photosensitive silver halide emulsion Em-G101.

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-2 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-3 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Subsequently, in the preparation of the emulsion EMP-103, the average particle size was changed in the same manner except that the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D) were changed. A monodispersed cubic emulsion EMP-104 having a 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

  A green-sensitive silver halide emulsion Em-G102 was prepared in the same manner as in the preparation of the green-sensitive silver halide emulsion Em-G101, except that EMP-104 was used instead of EMP-103. Em-G101 and Em -A green-sensitive silver halide emulsion using a 1: 1 mixture of G102 in the fifth layer.

(Preparation of red-sensitive silver halide emulsion)
The prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R101.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
Next, the prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R102.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 2 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
A 1: 1 mixture of the red-sensitive silver halide emulsion Em-R101 and the red-sensitive silver halide emulsion Em-R102 prepared above was used as the red-sensitive silver halide emulsion for the third layer.

  Details of the additives used in the preparation of each of the above photosensitive silver halide emulsions are as follows.

STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-4: p-Toluenethiosulfonic acid

[Production of Samples 102 to 108]
In the preparation of the sample 101, the yellow coupler (Y-1, Y-2, Y-3) of the seventh layer (blue photosensitive layer) is equivalent to 65% in terms of moles to the yellow coupler shown in Table 2. Samples 102 to 108 were produced in the same manner except that the amount added was equivalent to 75%.

[Production of Samples 109 to 116]
In the preparation of the samples 101 to 108, the dye-forming coupler represented by the general formula (a) was added to the seventh layer (blue-sensitive layer) at a ratio to the total yellow couplers described in Table 2, and Samples 109 to 116 were prepared in the same manner except that the white background conditioners (W1, W2) were removed.

[Preparation of Samples 117 and 118]
In the preparation of the sample 104, the dye-forming coupler represented by the general formula (a) (Exemplary Compound (14)) was added to the seventh layer (blue photosensitive layer) at a ratio to the total yellow couplers described in Table 2. Samples 117 and 118 were produced in the same manner except that.

《Image formation》
[Exposure equipment]
A drum exposure type exposure apparatus having the following light source was used.

  The exposure apparatus arranges 10 LEDs of B as a light source in the main scanning direction, and adjusts so that the same place can be exposed by 10 LEDs by delaying the exposure timing little by little, and also in the sub scanning direction. An exposure head was prepared in which 10 LEDs were arranged and exposure for 10 adjacent pixels could be performed at once. Similarly, for G and R, exposure heads were prepared by combining LEDs.

  The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 100 μm. The exposure time per pixel was about 100 nanoseconds.

  Using the above-described exposure apparatus, the yellow light source was exposed using the B light source at an exposure amount that would give a density that would minimize the color difference between the sample and the print target described later for each sample. Further, the magenta single color was also exposed with an exposure amount at which the color difference from the print target was minimized for each sample.

[Development processing]
The exposed sample was subjected to the development processing conditions shown below using an automatic developing machine.

Processing process Processing temperature Processing time Replenishment amount (ml / m ² )
Color development 38.0 ± 0.3 ° C 120 seconds 80ml
Bleach fixing 38.0 ± 0.5 ℃ 90 seconds 120ml
Stabilization 30-34 ° C 60 seconds 280ml
Drying 60 to 80 ° C. 30 seconds The treatment liquids used in the above treatment steps are as follows.

<Color developer tank solution and replenisher>
Tank liquid Replenisher Pure water 800ml 800ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (β-hydroxyethyl) -4-aminoaniline sulfate
2.9g 4.8g
N, N-disulfoethylhydroxylamine 20.4 g 18.0 g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
2.0g 2.5g
Potassium carbonate 30g 30g
Water was added to adjust the total volume to 1 liter, the tank solution was adjusted to pH = 10.0, and the replenisher solution was adjusted to pH = 10.6.

<Bleach fixer tank solution and replenisher>
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Water was added to make the total volume 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing liquid tank liquid and replenisher liquid>
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Zinc sulfate 0.5g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

<Evaluation of formed image>
The density at the maximum exposure amount of the yellow dye image thus obtained and the color difference at the exposure amount that minimizes the color difference from the target were evaluated.

[Measurement of maximum concentration]
The maximum density (Dmax) was measured with a blue filter using an X-Rite 508 type densitometer. For the spectral characteristics, status T was used.

[Measurement of minimum color difference]
The color difference from the target was measured using a spectrocolorimeter CM-2022 manufactured by Minolta Co., Ltd., and measured with a geometric condition d-0 for illumination and light reception, using a xenon pulse light source, and light D50 of 2 ° visual field auxiliary standard. The value of L ^* a ^* b ^* was determined, and the color difference was calculated.

Subsequently, the obtained dye image was obtained by using a spectrocolorimeter CM-2022 manufactured by Minolta Co., Ltd., to determine the value of L ^* a ^* b ^* at each density point where the color difference was minimum, and the minimum color difference The value (ΔE ^* ab) was calculated. As a color target, Japan Printing Industrial Machinery Manufacturers Association, ISO / TC130 National Committee, Japan Color Reproduction Printing 2001, art paper, ISO12647 pattern Y100% was used. Note that the smaller the minimum difference (ΔE ^* ab), the closer to the target color.

[Evaluation of white background]
About the white background part after the development processing of each sample, the following four kinds of fluorescent tubes are arranged at 15 cm intervals, arranged at a height of 2.5 m, and on a desk with a height of 75 cm, 50 people Visual evaluation by an evaluator was performed to evaluate a white background under a different light source.

<Observation light source>
A: Fluorescent lamp manufactured by Toshiba Corporation, Mellow White, FL40S / N type (day white / color temperature 5000K)
B: Matsushita Electric Co., Ltd. high color rendering fluorescent lamp, Realx, FL40S / L-EDL type (color rendering AAA / bulb color / color temperature 2700K)
C: Toshiba Corporation, D65 fluorescent lamp for color comparison / inspection, FL40S / D-EDL-D65 type (color rendering AAA / day white / color temperature 6500K)
D: Toshiba Corporation, Neoline Deluxe, FL40S / N-SDL type (color rendering AA / day white / color temperature 5000K)
<Evaluation>
Each sample was evaluated according to the following evaluation criteria, and an average value of 50 evaluators was obtained.

5: Observed in the same white color tone between each observation light source 4: Observed in almost the same white color tone between each observation light source 3: White background slightly different among some observation light sources Although it is observed in the color tone, it is within a practically acceptable range. 2: Observed in a different white color tone between several types of observation light sources, there is a problem in practical use 1: Clearly between all the observation light sources The results obtained as described above are shown in Table 2.

  As apparent from the results in Table 2, samples 102 to 108 and 110 to 118 using pyrimidin-4-one type and thiadiazine dioxide type yellow couplers represented by Y-4 to Y-6 are as follows: It can be seen that the color reproducibility of the yellow image is sufficiently approximated as a color proof. However, samples 110 to 118 using the dye-forming coupler represented by the general formula (a) of the present invention are preferable in terms of light source dependency on a white background. Furthermore, the samples 110 to 116 in which the white background adjusting agents (W1, W2) are not present are preferable as a white background with less light source dependency, and further, the color reproducibility of a single yellow color is more preferable in terms of the degree of approximation to the print target. It can be easily understood from the results of the samples 110 to 116 with respect to the samples 102 to 108 and 117 and 118.

Example 2
<< Preparation of silver halide color photosensitive material >>
[Preparation of Samples 121 to 127]
Samples 121 to 127 were prepared in the same manner as in the preparation of Sample 101 except that the magenta couplers (M-1, M-2) of the third layer (red photosensitive layer) were replaced with the magenta couplers described in Table 3. Was made.

[Production of Samples 128 to 134]
In the preparation of the above samples 121 to 127, the dye-forming coupler represented by the general formula (M1) or (M2) was added to the third layer (red photosensitive layer) in a ratio to the total magenta couplers described in Table 3. Further, samples 128 to 134 were produced in the same manner except that the white layer adjusting agent (W1, W2) of the eighth layer was further removed.

《Image formation》
[Exposure equipment]
Nippon Printing Sangyo Co., Ltd. as a printing target using the drum exposure type exposure apparatus described in Example 1, using an R light source to obtain a magenta monochromatic image, and an R and B light source to obtain a red image. Created by the Japan Machinery Manufacturers Association, ISO / TC130 National Committee, Japan Color Color Reproduction Printing 2001, Art Paper, M100% of ISO12647 pattern, 100% red, and density that minimizes the color difference with the print target for each sample Except that the exposure was performed with the exposure amount, the exposure was performed in the same manner as in Example 1.

<< Evaluation of development process and formed image >>
Samples 121 to 134 produced above and Samples 101 and 109 produced in Example 1 were exposed according to the above method and developed by the method described in Example 1, and then the resulting magenta color image, red For the image and the white background, the maximum density, the minimum value of the color difference, and the white background of the magenta image and the red image were evaluated in the same manner as described in Example 1, and the obtained results are shown in Table 3.

  As apparent from the results in Table 3, samples 128 to 134 using the dye-forming coupler represented by the general formula (M1) or (M2) of the present invention are represented by the general formula ( It turns out that it is very preferable with respect to the sample 101 which does not use the dye formation coupler represented by M1) or (M2), and 121-127. In addition, it is preferable that the samples 128 to 134 having no white background adjusting agent are more preferable in terms of the color reproducibility of the magenta single color and the degree of approximation to the print target. It can be easily understood from the results. Furthermore, also in red color reproduction, it appears remarkably as a result of the samples 128 to 134 in which the dye-forming coupler represented by the general formula (M1) or (M2) is added and no color tone adjusting agent is present.

Example 3
For each sample prepared in Example 1 and Example 2, the yellow illuminance image, the magenta monochrome image that was exposed and developed in the same manner as in Example 1 and Example 2, and the non-image portion that was processed unexposed, As a result of evaluating image storability (fading and stain generation) for each sample processed for 45 days with a 6,000 Lux fluorescent lamp tester and a thermostat of 50 ° C. and 80% RH, the composition of the present invention is obtained. It was confirmed that the silver halide color light-sensitive material was excellent in fading resistance in the color image area and stain resistance in the white background area.

Claims (10)

A dye-forming coupler, which is a compound represented by the following general formula (a):

[Wherein, R represents a substituent, and Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —N—C═N part. R 'represents a substituent, n represents an integer of 0 to 4, and X represents a hydrogen atom or a substituent. A represents an atomic group which is desorbed when coupled with a hydrogen atom or an oxidized form of a color developing agent and has a specific spectral absorption in the visible light region. ] The Z in the general formula (a) is a residue forming a 3H-pyrimidin-4-one ring or a residue forming a 1H-pyrimidin-4-one ring. Dye-forming coupler. Z in the general formula (a) is a residue forming a 2H- [1,2,4] thiadiazine-1,1-dioxide ring, or 4H- [1,2,4] thiadiazine-1,1-dioxide The dye-forming coupler according to claim 1, wherein the dye-forming coupler is a residue that forms a ring. A dye-forming coupler, which is a compound represented by the following general formula (M1).

[Wherein, R ₁₁ and R ₁₂ each represent a substituent, and Y ₁ represents an atomic group which is eliminated when coupled with an oxidized form of a color developing agent and has a specific spectral absorption in the visible light region. ] A dye-forming coupler, which is a compound represented by the following general formula (M2).

[Wherein, R ₂₁ and R ₂₂ each represent a substituent, and Y ₂ represents an atomic group which is eliminated when coupled with an oxidized form of a color developing agent and has a specific spectral absorption in the visible light region. ] In the silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on the reflective support, the yellow image forming layer is A silver halide color photographic material comprising a dye-forming coupler represented by the formula (a). In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the magenta image forming layer is A silver halide color light-sensitive material comprising a dye-forming coupler represented by the formula (M1). In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the magenta image forming layer is A silver halide color light-sensitive material comprising a dye-forming coupler represented by the formula (M2). In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the reflective support and the non-color-forming colloid 9. The silver halide color photosensitive material according to claim 6, wherein none of the layers contains a coloring substance remaining after color development. In a silver halide color light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer, and non-color-forming colloid layer on a reflective support, the yellow image forming layer and the magenta image The silver halide color photosensitive material according to any one of claims 6 to 9, wherein the forming layer and the cyan image forming layer do not contain a pigment or an oil-soluble dye.