JP2006091796A - Silver halide color photographic photosensitive material and method of image forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic photosensitive material excellent in color reproducibility and image preservability even in rapid processing. <P>SOLUTION: The silver halide color photographic photosensitive material has on a support at least one of each of yellow, magenta and cyan dye forming silver halide emulsion layers and at least one non-photosensitive hydrophilic colloid layer, wherein one of dye forming couplers is a dye forming coupler capable of forming an azomethine dye whose solubility in ethyl acetate is in the range of 1×10<SP>-8</SP>-5×10<SP>-3</SP>mol/l, the dye forming coupler is contained in an amount of 18-100 mass% based on a total lipophilic component, and one of the compounds represented by formula (I) is contained in the one non-photosensitive hydrophilic colloid layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material and an image forming method, and more particularly to a silver halide color photographic light-sensitive material and an image forming method capable of providing an image having excellent image storage stability.

Silver halide photographic light-sensitive materials have been widely used to date to provide high-quality images with stable quality at low cost, but demands for higher image quality, quality stabilization, and higher productivity by users. Is growing more and more. Improvements in whiteness, color reproducibility, sharpness, etc. are required in response to the demand for higher image quality. There is a need to improve stability during storage over time and performance stability during development processing. In addition, rapid processing is strongly required for improving productivity.
In photographic light-sensitive materials used for direct viewing such as color paper and color reversal, color reproducibility is important first. For improving color reproducibility, a dye-forming coupler (hereinafter also simply referred to as a coupler) and an oxidized form of an aromatic primary amine compound (more specifically, an oxidized form of a p-phenylenediamine color developing agent) There is little unnecessary absorption of the pigment itself formed by the coupling reaction, and it is necessary to have excellent absorption characteristics. In addition, it is important that there are few residual colors such as sensitizing dyes and irradiation preventing dyes, and that there is little fogging. Second, it is important to have high image storage stability after color image formation. For this reason, the selection of couplers and high-boiling organic solvents used in this industry as well as the use of image stabilizers to effectively suppress the degradation of dyes by light and heat and to stabilize color images for a long period of time Has been made.
In the recent photo processing service industry, color printing from digital information sources such as digital cameras can be obtained easily and quickly due to the spread of printing equipment using digital exposure, and there is an opportunity for image output by color printing. It is increasing. In the color printing industry, there is a demand for efficiency such as shortening the time from print exposure to color development processing mainly for the purpose of increasing the production speed of laboratories and improving the service to customers. General means for improving rapid development processability in color photographic light-sensitive materials include, for example, [1] reduction of the amount of organic material applied by adopting a coupler having a large molecular extinction coefficient of a coloring dye, and [2] associated with [1]. Reduction of silver halide emulsion coating amount, reduction of hydrophilic binder coating amount associated with [3] [1] and thinning of the entire photographic composition layer, [4] Adoption of highly active coupler, [5] Development For example, a silver halide emulsion having a high speed can be used. In order to provide a light-sensitive material suitable for ultra-rapid processing in color development and desilvering, the industry has attempted to reduce the amount of silver applied to the light-sensitive material by using couplers that form dyes with a high molecular extinction coefficient. Efforts have been made to the above [1] and [2] in order to prevent unnecessary processing solution components from remaining in the print after processing and causing stains.

As couplers having high activity and molecular extinction coefficient and suitable for the above light-sensitive materials, as couplers improved from acylacetanilide, 1-alkylcyclopropanecarbonylacetate anilide compounds (see Patent Document 1) and cyclic malondiamide type yellow couplers. (Refer to Patent Document 2), heterocyclic acetanilide yellow coupler (refer to Patent Document 3), pyrazoloazole magenta coupler (refer to Patent Document 4 and Patent Document 5), pyrroloazole type cyan coupler (refer to Patent Document 6 and Patent Document 7) And pyrrolotriazole type cyan couplers (see Patent Document 8 and Patent Document 9).
However, for the purpose of further reducing the coating amount of the organic material and reducing the entire thickness of the photographic composition layer to further improve the rapid processability, a coupler that forms a dye having a high molecular extinction coefficient as described above can be used. However, this has not always been sufficient. As organic materials other than couplers, for example, by reducing the high boiling point organic solvent and reducing the gelatin binder together with it, a photosensitive material suitable for the water washing process and drying process in ultra-rapid processing can be obtained. Or, the image storage stability may be impaired.

Japanese Patent Laid-Open No. 4-218,042 JP-A-5-11416 JP 2003-173007 A JP-A-63-041851 Japanese Patent Laid-Open No. 06-043611 European Patent Publication EP0488248A1 Specification European Patent Publication No. EP 0291197 A1 JP 2001-342189 A JP 2002-287111 A

  The present invention has been made in view of the above, and an object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility and image storage and an image forming method, and further, rapid processing. An object is to provide a silver halide color photographic light-sensitive material having excellent suitability and an image forming method.

The inventors of the present invention have made extensive studies and found that the above problems can be achieved by the following configuration, and have achieved the object. That is, the present invention is as follows.
(1) A yellow dye-forming coupler-containing photosensitive silver halide emulsion layer, a magenta dye-forming coupler-containing photosensitive silver halide emulsion layer, a cyan color-forming coupler-containing photosensitive silver halide emulsion layer, and a non-photosensitive hydrophilic layer Silver halide color photographic light-sensitive material having at least one conductive colloid layer, wherein at least one dye-forming coupler has a solubility in ethyl acetate due to a reaction with an oxidized form of an aromatic primary amine compound. A dye-forming coupler that forms an azomethine dye of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less, wherein the dye-forming coupler is used as a total lipophilic component of the layer containing the dye-forming coupler. And contained in the following general formula (I) in at least one layer of the non-photosensitive hydrophilic colloid layer. The silver halide color photographic material, wherein at least one is contained in the compound.

In general formula (I), R ^{21 to} R ²⁹ may be the same or different and each represents a hydrogen atom or a substituent. However, at least one of R ^{21 to} R ²⁹ is a substituent. R ^{21 to} R ²⁹ may be a divalent group, and may be combined with a dimer or other monomer or a polymer chain to form a monopolymer or a copolymer.
(2) The silver halide color as described in (1), wherein the solubility of the azomethine dye in ethyl acetate is 1 × 10 ⁻⁸ mol / L or more and 7 × 10 ⁻⁴ mol / L or less. Photosensitive material.
(3) The silver halide emulsion layer containing at least one dye-forming coupler for forming the azomethine dye has a total dye-forming coupler coating amount of from 0.18 mmol / m ^{2 to} 0.28 mmol / m ² . The silver halide color photographic light-sensitive material as described in (1) or (2), wherein the maximum optical reflection density at the maximum absorption wavelength of the dye after dye formation is 2.0 or more.
(4) The silver halide color photographic light-sensitive material as described in any one of (1) to (3), wherein the maximum absorption wavelength of the azomethine dye is from 570 nm to 700 nm.
(5) The halogen according to any one of (1) to (4), wherein the dye-forming coupler that forms the azomethine dye is a coupler represented by the following general formula (CP-I): Silver halide color photographic material.

In the general formula (CP-I), G _a is -C (R ₂₃₎ = or represents -N =, G _b when G _a represents -N = is -C (R ₂₃₎ = represents, G _a There G _b to represent a -C (R ₂₃₎ = represents -N =. R ₂₁ and R ₂₂ each independently represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more and 1.0 or less. R ₂₃ represents a substituent. Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.
(6) Any of (1) to (5), wherein the silver halide color photographic light-sensitive material contains at least one selected from dye-forming couplers represented by the following general formula (Y): 2. A silver halide color photographic light-sensitive material as described in item 1.

In General Formula (Y), Q represents a nonmetallic atom group that forms a 5- to 7-membered ring with —N═CN (R1) —. R1 represents a substituent. R2 represents a substituent. m represents an integer of 0 or more and 5 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.
(7) The oxidant of the aromatic primary amine compound is an oxidant of 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline ( The silver halide color photographic light-sensitive material according to any one of 1) to (6).
(8) The dye-forming coupler that forms the azomethine dye contains 24% by mass to 80% by mass with respect to the total lipophilic component in the layer containing the dye-forming coupler (1) The silver halide color photographic light-sensitive material according to any one of to (7).
(9) A yellow dye-forming coupler-containing photosensitive silver halide emulsion layer, a magenta dye-forming coupler-containing photosensitive silver halide emulsion layer, a cyan dye-forming coupler-containing photosensitive silver halide emulsion layer, and a non-photosensitive hydrophilic layer An image forming method for developing a silver halide color photographic light-sensitive material having at least one conductive colloid layer after exposure, wherein at least one of the dye-forming couplers reacts with an oxidized form of an aromatic amine compound To form an azomethine dye having a solubility in ethyl acetate of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less, and the silver halide color photographic light-sensitive material forms the azomethine dye. The dye-forming coupler is contained in an amount of 18% by mass to 100% by mass with respect to the total lipophilic component of the layer containing the dye-forming coupler. Image forming method characterized by comprising at least one compound represented by the following general formula in at least one layer of the non-light-sensitive hydrophilic colloid layer (I) to.

In general formula (I), R ^{21 to} R ²⁹ may be the same or different and each represents a hydrogen atom or a substituent. However, at least one of R ^{21 to} R ²⁹ is a substituent. R ^{21 to} R ²⁹ may be a divalent group, and may be combined with a dimer or other monomer or a polymer chain to form a monopolymer or a copolymer.
(10) The silver halide emulsion layer containing at least one dye-forming coupler for forming the azomethine dye has a total dye-forming coupler coating amount of from 0.18 mmol / m ^{2 to} 0.28 mmol / m ² . The image forming method as described in (9) above, wherein the maximum optical reflection density at the maximum absorption wavelength of the dye after dye formation is 2.0 or more.
(11) The image forming method according to (9) or (10), wherein the color development time is 30 seconds or less in the development processing.
(12) The image forming method according to any one of (9) to (11), wherein the exposure is 1 × 10 ⁻⁴ seconds or less.

  According to the silver halide color photographic light-sensitive material and image forming method of the present invention, a photograph excellent in color reproducibility and image storability even in rapid processing, particularly a color print can be produced.

The present invention is described in detail below.
The present invention relates to a light-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, a light-sensitive silver halide emulsion layer containing a cyan color-forming coupler, and a non-photosensitive material. A silver halide color photographic light-sensitive material having at least one hydrophilic colloid layer, wherein at least one of the dye-forming couplers is converted into ethyl acetate by reaction with an oxidized form of an aromatic primary amine compound. It contains a dye-forming coupler that forms an azomethine dye having a solubility of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less (hereinafter also referred to as an organic solvent poorly soluble dye).
Here, the solubility in ethyl acetate refers to the molar molar concentration (the solute mol amount contained in 1000 cm ³ of the saturated solution) at normal temperature (20 to 25 ° C., 25 ° C. if specified). The solubility is preferably determined according to a general operation, that is, preparation of a saturated solution that has reached dissolution equilibrium, separation of the solid phase and the liquid layer, and determination of the solute in the liquid phase. "New Experimental Chemistry Course (Maruzen Co., Ltd.)" etc.
A preferable range of the solubility of the dye in ethyl acetate is 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less, and more preferably 1 × 10 ⁻⁸ mol / L or more and 2 × 10. ⁻³ mol / L or less, more preferably 1 × 10 ⁻⁸ mol / L or more and 7 × 10 ⁻⁴ mol / L or less, and most preferably 1 × 10 ⁻⁶ mol / L or more and 5 × 10 ^−4. mol / L or less.

In the present invention, the above-mentioned dye-forming coupler that forms a poorly soluble dye in an organic solvent is 18% by mass or more and 100% by mass with respect to the total lipophilic component of the layer containing the coupler (coloring layer containing the coupler). Contains below.
Here, the lipophilic component is a hydrophobic substance composed of a coupler, a high boiling point organic solvent, a water-insoluble and organic solvent-soluble polymer, and a water-insoluble organic material added for the purpose of image stabilization, color mixing prevention and stain prevention. And represents an organic solvent-soluble composition. The lipophilic component comprising these organic solvent-soluble compositions can generally be obtained as a fine particle dispersion in a hydrophilic binder such as gelatin. The dye-forming coupler that forms the organic solvent poorly soluble dye is preferably contained in an amount of 18% by mass or more and 99% by mass or less, and 18% by mass or more and 90% by mass or less, based on the total lipophilic component of the layer containing the coupler. It is more preferable to contain, and it is most preferable to contain 24 mass% or more and 80 mass% or less.

In the present invention, the above-mentioned dye-forming coupler that forms a dye hardly soluble in an organic solvent can be used alone or in combination with other dye-forming couplers in the silver halide emulsion layer to be used. When other dye-forming couplers are used in combination, the solubility of the dyes formed by the other dye-forming couplers in ethyl acetate is not particularly limited to the above preferred range. In the combined use of the above-mentioned dye-forming couplers, all of the dye-forming couplers used together form an azomethine dye having a solubility in ethyl acetate of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less. The use ratio may be any ratio. On the other hand, when the coupler that forms an azomethine dye having a solubility in ethyl acetate of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less does not belong to the preferred range of the solubility in ethyl acetate, Of the coupler (s) that form an azomethine dye having a total mole of these coupler (s) and solubility in ethyl acetate of from 1 × 10 ⁻⁸ mol / L to 5 × 10 ⁻³ mol / L The total molar ratio is preferably 6: 4 to 0:10, more preferably 5: 5 to 0:10, and most preferably 5: 5 to 1: 9.

The total amount of coupler coating in the silver halide emulsion layer containing at least one dye-forming coupler that forms a poorly soluble dye in an organic solvent is preferably smaller from the viewpoint of thinning, but after the dye image formation, The optical reflection density at the maximum absorption wavelength (maximum absorption wavelength of the dye obtained from the dye-forming coupler that forms the organic solvent hardly soluble dye) is preferably at least 1.8 (preferably 1.8 or more and 2.6 or less). 2.0 or more (preferably 2.0 or more and 2.5 or less), more preferably 2.1 or more (preferably 2.1 or more and 2.4 or less).
Specifically, the coating amount of the dye-forming coupler for obtaining such reflection density is preferably 0.16 mmol / m ² or more and 0.30 mmol / m ² or less, more preferably 0.18 mmol / m ² or more and 0.28. more preferably not more than mmol / m ^2, most preferably 0.19 mmol / m ² or more 0.26 mmol / m ² or less.

  In the present invention, the melting point of the organic solvent poorly soluble dye is preferably higher than the melting point of the dye-forming coupler that forms the dye. Specifically, the organic solvent poorly soluble dye preferably has a high melting point of 0 ° C. or higher, more preferably 30 ° C. or higher, and most preferably 60 ° C. or higher with respect to the dye-forming coupler.

The dye-forming coupler for forming the organic solvent hardly soluble dye may be any, but in the present invention, it is preferably a cyan dye-forming coupler, and the maximum absorption wavelength of the dye at the time of image formation is the photographic composition layer. Among them, it is preferably 570 nm or more and 700 nm or less, and more preferably 580 nm or more and 660 nm or less.
Examples of couplers that form such cyan dyes include dye couplers represented by the following general formula (CP-I).

In the general formula (CP-I), G _a is -C (R ₂₃₎ = or represents -N =, G _b when G _a represents -N = is -C (R ₂₃₎ = represents, G _a There G _b to represent a -C (R ₂₃₎ = represents -N =. R ₂₃ represents a substituent. Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer. R ₂₁ and R ₂₂ are both electron-withdrawing groups having Hammett's substituent constant σ _p value of 0.20 or more and 1.0 or less, but the sum of σ _p values of R ₂₁ and R ₂₂ is 0.65 or more. It is desirable that The coupler used in the present invention has excellent performance as a cyan coupler by introducing such a strong electron-withdrawing group. The sum of the σ _p values of R ₂₁ and R ₂₂ is preferably 0.70 or more, and the upper limit is about 1.8.

In the present invention, R ₂₁ and R ₂₂ are electron withdrawing groups having Hammett's substituent constant σ _p value (hereinafter simply referred to as σ _p value) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less. Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σ _p value and a σ _m value, and these values are described in many general books. A. Dean ed. “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Chemical Areas Extra”, 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, Pp. 165-195, detailed in 1991. In the present invention, R ₂₁ and R ₂₂ are defined by Hammett's substituent constant σ _p value, but this does not mean that the value is limited only to a certain substituent having a known value described in these documents. Of course, even if the document is unknown, it is included as long as it is included in the range when measured based on Hammett's law.

Specific examples of R ₂₁ and R ₂₂ which are electron withdrawing groups having a σ _p value of 0.20 or more and 1.0 or less include acyl group, acyloxy group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, Cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group A thiocarbonyl group, an alkyl group substituted with at least two halogen atoms, an alkoxy group substituted with at least two halogen atoms, an aryloxy group substituted with at least two halogen atoms, at least 2 A substituted with one or more halogen atoms An alkylthio group substituted with at least two or more halogen atoms, an aryl group substituted with another electron-withdrawing group of σ _p 0.20 or more, a heterocyclic group, a chlorine atom, a bromine atom, an azo group, Or a selenocyanate group is mention | raise | lifted. Of these substituents, the group that can further have a substituent may further have a substituent as described for R ₂₃ described later.

  The aliphatic oxycarbonyl group may be linear, branched or cyclic, and the aliphatic site may be saturated or may contain an unsaturated bond. , Alkoxycarbonyl, cycloalkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkenyloxycarbonyl and the like.

When typical sigma _p value is listed sigma _p value of the electron withdrawing groups 0.2 to 1.0, a bromine atom (0.23), chlorine atom (0.23), a cyano group (0.66 ), Nitro group (0.78), trifluoromethyl group (0.54), tribromomethyl group (0.29), trichloromethyl group (0.33), carboxyl group (0.45), acetyl group ( 0.50), benzoyl group (0.43), acetyloxy group (0.31), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), Methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37 ) Emissions sulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), a sulfamoyl group (0.57), and the like.

R ₂₁ is preferably a cyano group, an aliphatic oxycarbonyl group (a linear or branched alkoxycarbonyl group having 2 to 36 carbon atoms, an aralkyloxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, a cycloalkoxycarbonyl group, a cycloalkoxy group, An alkenyloxycarbonyl group, such as methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, 2-ethylhexyloxycarbonyl, sec-butyloxycarbonyl, oleyloxycarbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyl Oxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), dialkyl Suphono group (C2-C36 dialkylphosphono group such as diethylphosphono, dimethylphosphono), alkyl or arylsulfonyl group (C1-C36 alkyl or arylsulfonyl group such as methanesulfonyl Group, a butanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group), a fluorinated alkyl group (a fluorinated alkyl group having 1 to 36 carbon atoms, such as trifluoromethyl). R ₂₁ is particularly preferably a cyano group, an aliphatic oxycarbonyl group, or a fluorinated alkyl group.

R ₂₂ is preferably an aliphatic oxycarbonyl group or a carbamoyl group (a carbamoyl group having 1 to 36 carbon atoms such as diphenylcarbamoyl or dioctylcarbamoyl), a sulfamoyl group (1 to 36 carbon atoms), as exemplified in R _21. of a sulfamoyl group, e.g., dimethylsulfamoyl, dibutylsulfamoyl), a dialkyl phosphono group as mentioned in R _21, a diaryl phosphono group diarylphosphono group (12 to 50 carbon atoms, e.g. Diphenylphosphono, di (p-toluyl) phosphono).

R ₂₃ is preferably selected from an aliphatic group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, arylthio group, alkylthio group, ureido group, alkoxycarbonylamino group, carbamoyloxy group, and heterocyclic thio group. These substituents are preferable, and these may further have a substituent. R ₂₃ is more preferably an aliphatic group (preferably an alkyl group or an aralkyl group), an aryl group, an alkoxy group or an acylamino group, which may be further substituted.

  Y is preferably a hydrogen atom, a halogen atom, an aryloxy group, a heterocyclic acyloxy group, a dialkylphosphonooxy group, an arylcarbonyloxy group, an arylsulfonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. Further, it is also preferable that the leaving group or the compound released from the leaving group further has a property of reacting with an oxidized developer (preferably an oxidized aromatic primary amine color developing agent). For example, a leaving group may be a non-color-forming coupler, a hydroquinone derivative, an aminophenol derivative, a sulfonamide phenol derivative, or the like.

  The coupler represented by the general formula (CP-I) is preferably represented by the following general formula (CP-II).

In the general formula (CP-II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a ring structure together with carbon atoms at both ends, and the nonmetallic atom group formed by Z may be substituted with a substituent. X represents a hydrogen atom or a substituent. R ¹⁶ , R ¹⁹ and R ²⁰ may be the same or different and each represents a hydrogen atom or a substituent. R ¹⁷ represents an acylamino group, a substituted or unsubstituted amino group, an alkoxycarbonylamino group, a ureido group, or a nitrogen-containing heterocyclic group bonded with a nitrogen atom. R ¹⁸ represents an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acylamino group, a substituted or unsubstituted amino group, an alkoxycarbonylamino group, a ureido group, or a nitrogen-containing heterocyclic group bonded with a nitrogen atom. R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ may be bonded to each other to form a 5- to 8-membered ring.

Hereinafter, the coupler represented by the general formula (CP-II) will be described in detail.
In the general formula (CP-II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom or a substituent. The substituent is not particularly limited as long as it is substitutable, and is preferably a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aryl group, and more preferable are those described below.
R ¹¹ and R ¹² preferably represent an aliphatic group, for example, a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group. Specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl, tridecyl, cyclopentyl, and cyclohexyl are represented. More preferably, it is C1-C12 as an aliphatic group.
R ¹³ , R ¹⁴ and R ¹⁵ are preferably a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups listed above for R ¹¹ and R ¹² . R ¹³ , R ¹⁴ and R ¹⁵ are particularly preferably a hydrogen atom.

In the general formula (CP-II), Z represents a nonmetallic atom group necessary for forming a ring structure together with carbon atoms at both ends, and the nonmetallic atom group (ring) formed by Z is substituted with a substituent. May be. The ring formed by Z is preferably a 5- to 8-membered ring, and may be a saturated ring or may have an unsaturated bond. Preferable nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms or carbon atoms, and more preferably carbon atoms.
Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a piperazine ring, an oxane ring, a thiane ring, and the like. May be substituted.
The ring formed by Z is preferably a cyclohexane ring which may be substituted, and particularly preferably, the 4-position is substituted with an alkyl group having 1 to 24 carbon atoms (which may be further substituted with a substituent). Cyclohexane ring.

In general formula (CP-II), X represents a hydrogen atom or a substituent. The substituent is preferably a group that promotes the elimination of the X—C (═O) O— group during the oxidative coupling reaction. Among them, X preferably represents a heterocyclic ring, a substituted or unsubstituted amino group, or an aryl group. The heterocycle is preferably a 5- to 8-membered ring having a nitrogen atom, an oxygen atom or a sulfur atom and having 1 to 36 carbon atoms. More preferably, it is a 5-membered or 6-membered ring bonded by a nitrogen atom, of which a 6-membered ring is particularly preferable. These rings may form a condensed ring with a benzene ring or a hetero ring. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine, pyrazolidine, thiazolidine, pyrazoline, and compounds in which these substituents are substituted. Preferred substituents in this case include alkyl groups, alkenyl groups, acylamino groups, alkylsulfonamide groups, arylsulfonamide groups, and the like. Preferred examples of the substituted amino group include an aliphatic group, an aryl group, and a heterocyclic group. The substituted amino group is preferably disubstituted rather than monosubstituted. The aliphatic group may be linear, branched or cyclic, and examples thereof include an alkyl group having 36 or less carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group. May be substituted with a halogen atom such as a cyano group, an alkoxy group (for example, methoxy), an alkoxycarbonyl group (for example, ethoxycarbonyl), chloro, a hydroxyl group, or a carboxyl group. As the aryl group, those having 6 to 36 carbon atoms are preferable, and a single ring is more preferable. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 2, 4-dichlorophenyl and the like can be mentioned.
X is particularly preferably a disubstituted amino group having an aliphatic group substituted with an alkoxycarbonyl group.

In the general formula (CP-II), R ¹⁶ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent. Preferably, hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, cyano group, nitro group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group , Arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio Group, sulfinyl group, phosphonyl group and azolyl group. More preferably hydrogen atom, alkyl group, halogen atom, aryl group, heterocyclic group, alkoxy group, cyano group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonylamino group, imide group, phosphonyl group, more preferably hydrogen atom, alkyl group, alkoxy group, acylamino group, alkoxycarbonylamino It is a group. Particularly preferred is a hydrogen atom.

In the general formula (CP-II), R ¹⁷ is an acylamino group (preferably an acylamino group having 2 to 36 carbon atoms which may have a substituent, for example, acetamide, t-butylamide, benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), substituted Or an unsubstituted amino group (preferably an alkylamino group having 1 to 36 carbon atoms which may have a substituent, for example, methylamino, butylamino, dodecylamino, diethylamino, N-methyl-N-butylamino, Optionally substituted anilino group having 6 to 36 carbon atoms such as phenylamino, 2-chloro Anilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-methylanilino, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) Dodecanamido} anilino), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 1 to 36 carbon atoms which may have a substituent such as methoxycarbonylamino), a ureido group (preferably having a substituent). A ureido group having 1 to 36 carbon atoms which may be, for example, 3, 3 dimethylureido, a nitrogen-containing heterocyclic group bonded with a nitrogen atom (preferably 5-8 which may have a substituent) Membered nitrogen-containing heterocycle, such as 1-pyrrolidinyl, 1-piperidyl, 1-piperazinyl, 4-morpholinyl, Ndrinyl).
R ¹⁷ is preferably an acylamino group or a nitrogen-containing heterocyclic group bonded with a nitrogen atom, and more preferably an acylamino group.

In the general formula (CP-II), R ¹⁸ is an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms which may have a substituent, for example, methoxy, ethoxy), an alkylthio group (preferably substituted). An alkylthio group having 1 to 36 carbon atoms which may have a group, for example, methylthio), an aryloxy group (preferably an aryloxy group having 6 to 36 carbon atoms which may have a substituent) , For example, phenoxy), an arylthio group (preferably an arylthio group having 6 to 36 carbon atoms which may have a substituent, for example, phenylthio), an acylamino group (preferably having a substituent). An acylamino group having 2 to 36 carbon atoms, such as acetamide, t-butylamide, benzamide, tetradecanamide, 2- (2,4-di-t Amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), a substituted or unsubstituted amino group (preferably a substituent) An alkylamino group having 1 to 36 carbon atoms which may have, for example, methylamino, butylamino, dodecylamino, diethylamino, N-methyl-N-butylamino, an optionally substituted carbon number 6-36 anilino groups such as phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-methylanilino, 2-chloro-5- { 2- (3-t-butyl-4-hydroxyphenoxy) dodecanamido} anilino) An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 1 to 36 carbon atoms which may have a substituent, for example, methoxycarbonylamino), a ureido group (preferably an optionally substituted group). A ureido group having 1 to 36 carbon atoms, such as 3, 3 dimethylureido, a nitrogen-containing heterocyclic group bonded with a nitrogen atom (preferably a nitrogen-containing 5- to 8-membered ring optionally having a substituent) A heterocycle, for example, 1-pyrrolidinyl, 1-piperidyl, 1-piperazinyl, 4-morpholinyl, indolinyl).
R ¹⁸ is preferably an alkoxy group, an aryloxy group or an amino group, more preferably an alkoxy group.

In the general formula (CP-II), R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ are bonded to each other, and a 5- to 8-membered ring (for example, an indoline ring together with the benzene ring) , A tetrahydronaphthalene ring).

  The coupler represented by the general formula (CP-II) is more preferably represented by the following general formula (CP-III).

In the general formula (CP-III), R ³¹ represents an alkyl group. R ³² represents an alkoxy group. R ³³ , R ³⁴ and R ³⁵ represent a hydrogen atom or an alkyl group. In the case of each alkyl group, R ³³ and R ³⁴ may be bonded to each other to form a 3- to 6-membered ring.

Hereinafter, the coupler represented by the general formula (CP-III) will be described in detail.
In the general formula (CP-I), an R ³¹ alkyl group (preferably an alkoxy group having 1 to 36 carbon atoms which may have a substituent, for example, methyl or ethyl) is represented. R ³¹ is more preferably an ethyl group. R ³² represents an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms which may have a substituent, for example, methoxy, ethoxy). R ³² is more preferably a methoxy group.

R ³³ , R ³⁴ and R ^{35 each} represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms which may have a substituent, for example, methyl, ethyl, chloromethyl). R ³³ , R ³⁴ and R ³⁵ are more preferably a methyl group.

In the general formula (CP-III), when R ³³ and R ³⁴ are each an alkyl group, it is preferable that they are bonded to each other to form a 3- to 6-membered ring (for example, a cyclopropyl ring).

Specific examples of the couplers represented by the general formula (CP-III) of the present invention (Exemplary Compounds CP- (1) to CP- (10)) are shown below, but are not limited thereto.

  The dye-forming coupler represented by the general formula (CP-I) can be easily synthesized by the method described in JP-A Nos. 2001-342189 and 2002-287111, or a method based thereon. .

The dye-forming coupler represented by the general formula (CP-I) is generally 0.01 to 1 g / m ² , preferably 0.05 to 0.4 g / m ² , more preferably 0.1 to 0. It is preferable to apply in an amount of ³ g / m ² .

  As yellow dye-forming couplers that can be used in the light-sensitive material of the present invention (in this specification, sometimes simply referred to as “yellow couplers”), in addition to the compounds described in Table 1 below, European Patent EP 0447969A1 An acylacetamide-type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group described in European Patent EP 0482552A1, a malondianilide-type yellow coupler having a cyclic structure described in EP 0 482 552 A1, European Patent No. 935870 A1, Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide couplers described in US Pat. No. 953871A1, No. 953872A1, No. 953833A1, No. 953874A1, No. 953875A1, etc. No. 5,118,599 Acylacetamide yellow couplers having a mounting been dioxane structure is preferably used. Among these, it is preferable to use an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring. These couplers can be used alone or in combination.

  In the light-sensitive material of the present invention, it is preferable that any one of the light-sensitive material constituting layers contains at least one dye-forming coupler represented by the following general formula (Y).

  In the formula, R1 represents a substituent other than a hydrogen atom. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, and a cyano group. Group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (alkylamino group, Anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, sulfonamido group (alkyl or arylsulfonylamino group), merca Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or hetero Examples thereof include a ring azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

  In addition, the above-described substituent may be further substituted with a substituent, and examples of the substituent include the above-described groups.

  Preferably, R1 is a substituted or unsubstituted alkyl group. The total carbon number of R1 is preferably 1 or more and 60 or less, more preferably 6 or more and 50 or less, further preferably 11 or more and 40 or less, and most preferably 16 or more and 30 or less. Examples of the substituent when R1 is a substituted alkyl group include the examples given as the substituent for R1 described above. Moreover, 1-40 are preferable, as for carbon number of the alkyl group itself of R1, 3-36 are more preferable, More preferably, it is 8-30. This preferred order is not particularly dependent on Q, but is particularly preferred when Q described below is a group represented by -C (-R11) = C (-R12) -CO-.

Preferably, R1 is an unsubstituted alkyl group having 11 or more carbon atoms, or an alkyl group substituted with an alkoxy group or an aryloxy group at the 2-position, 3-position or 4-position, and more preferably an unsubstituted alkyl group having 16 or more carbon atoms. An alkyl group, or an alkyl group substituted with an alkoxy group or an aryloxy group at the 3-position, and most preferably a C ₁₆ H ₃₃ group, a C ₁₈ H ₃₇ group, a 3-lauryloxypropyl group, or a 3- (2,4 -Di-t-amylphenoxy) propyl group.

In General Formula (Y), Q represents a nonmetallic atom group that forms a 5- to 7-membered ring with —N═C—N (R1) —. Preferably, the formed 5- to 7-membered ring is a substituted or unsubstituted, monocyclic or condensed heterocyclic ring, and more preferably, the ring constituent atoms are selected from a carbon atom, a nitrogen atom and a sulfur atom. More preferably, Q is -C (-R11) = C (-R12 ) -SO 2 - in, or -C (-R11) = C (-R12 ) -CO- represents a group represented by (the present invention The notation of these groups does not limit the direction of bonding of the groups represented by these groups). Among Preferably, Q is -C (-R11) = C (-R12 ) -SO 2 - represents a group represented by. R11 and R12 are bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently represents a hydrogen atom or a substituent. The formed 5- to 7-membered ring is a saturated or unsaturated ring, and the ring may be an alicyclic ring, an aromatic ring, or a heterocyclic ring. For example, a benzene ring, a furan ring, a thiophene ring, a cyclopentane ring And cyclohexane ring. Examples of the substituent include those exemplified as the substituent for R1 described above.

  The ring formed by bonding each of these substituents or a plurality of substituents may be further substituted with a substituent (including the groups exemplified as the substituent for R1 described above).

In the general formula (Y), R2 represents a substituent other than a hydrogen atom. Examples of this substituent include those listed as examples of the substituent for R1 described above. Preferably, R2 is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl, isopropyl), aryl group (eg, phenyl, naphthyl), alkoxy group (eg, methoxy, isopropyloxy), aryloxy group (Eg phenoxy), acyloxy group (eg acetyloxy), amino group (eg dimethylamino, morpholino), acylamino group (eg acetamido), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (eg methoxy Carbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), carbamoyl group (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-methyl) Rufamoyl, N, N-diethylsulfamoyl), alkylsulfonyl group (eg methanesulfonyl), arylsulfonyl group (eg benzenesulfonyl), alkylthio group (eg methylthio, dodecylthio), arylthio group (eg phenylthio, naphthylthio), cyano group , Carboxyl group and sulfo group. When R2 is in the ortho position with respect to the —CONH— group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylthio group, or an arylthio group is preferable.
In the present invention, it is preferable that at least one R2 is in an ortho position with respect to the —CONH— group.

In general formula (Y), m represents an integer of 0 or more and 5 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring.
m is preferably 0 to 3, more preferably 0 to 2, still more preferably 1 to 2, and most preferably 2.

In the general formula (Y), X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer. Examples of the group in which X is a group capable of leaving by a coupling reaction with an oxidized developer include a group leaving by a nitrogen atom, a group leaving by an oxygen atom, a group leaving by a sulfur atom, a halogen atom (for example, a chlorine atom) , Bromine atom) and the like.
The group leaving from the nitrogen atom is a heterocyclic group (preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic (in the present specification, means having 4n + 2 cyclic conjugated electrons). Or a non-aromatic, monocyclic or condensed heterocyclic group, and more preferably a ring-constituting atom is selected from a carbon atom, a nitrogen atom and a sulfur atom, and any one of a nitrogen atom, an oxygen atom and a sulfur atom 5 or 6-membered heterocyclic group having at least one heteroatom), for example, succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole Benzimidazole, benzotriazole, imidazoline-2,4-dione, o Sazolidine-2,4-dione, thiazolidine-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one , Indoline-2,3-dione, 2,6-dioxypurineparabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2 -Pyrazone, 2-amino-1,3,4-thiazolidin-4-one), carbonamide groups (eg acetamide, trifluoroacetamide), sulfonamido groups (eg methanesulfonamide, benzenesulfonamide), arylazo groups (eg Phenylazo, naphthylazo), carbamoylamino group (for example, N-methylcarbamoylamino) Etc., and the like.

  Of the groups leaving by a nitrogen atom, preferred are heterocyclic groups, and more preferred are aromatic heterocyclic groups having 1, 2, 3 or 4 nitrogen atoms as ring-constituting atoms, or the following general formula ( L) is a heterocyclic group represented.

In the formula, L represents a residue which forms a 5- to 6-membered nitrogen-containing heterocycle together with -NC (= O)-.
These examples are given in the description of the heterocyclic group, and these are more preferable. Among these, L is preferably a residue that forms a 5-membered nitrogen-containing heterocycle.

Examples of the group capable of leaving with an oxygen atom include aryloxy groups (eg, phenoxy, 1-naphthoxy), heterocyclic oxy groups (eg, pyridyloxy, pyrazolyloxy), acyloxy groups (eg, acetoxy, benzoyloxy), alkoxy groups (eg, methoxy, dodecyl). Oxy), carbamoyloxy group (for example, N, N-diethylcarbamoyloxy, morpholinocarbamoyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), alkoxycarbonyloxy group (for example, methoxycarbonyloxy, ethoxycarbonyloxy), alkylsulfonyl Examples thereof include an oxy group (for example, methanesulfonyloxy) and an arylsulfonyloxy group (for example, benzenesulfonyloxy, toluenesulfonyloxy).
Of the groups leaving by an oxygen atom, preferred are an aryloxy group, an acyloxy group, and a heterocyclic oxy group.

Examples of the group that leaves with a sulfur atom include an arylthio group (for example, phenylthio, naphthylthio), a heterocyclic thio group (for example, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxazolylthio, benzimidazolylthio), Examples include alkylthio groups (for example, methylthio, octylthio, hexadecylthio), alkylsulfinyl groups (for example, methanesulfinyl), arylsulfinyl groups (for example, benzenesulfinyl), arylsulfonyl groups (for example, benzenesulfonyl), alkylsulfonyl groups (for example, methanesulfonyl), and the like. .
Of the groups leaving with a sulfur atom, preferred are an arylthio group and a heterocyclic thio group, with a heterocyclic thio group being more preferred.

X may be substituted with a substituent, and examples of the substituent for substituting X include those listed as examples of the substituent for R1.
X is preferably a group capable of leaving by a coupling reaction with an oxidant of a developing agent, and among these leaving groups, a group that is preferably released by a nitrogen atom, a group that is released by an oxygen atom, and a group that is released by a sulfur atom More preferably, it is a group capable of leaving by a nitrogen atom, and more preferably in the order of the preferred groups described in terms of a group leaving by a nitrogen atom.
Further explaining the preferable group of X, a group leaving by a nitrogen atom is preferable, but an aromatic heterocyclic group having at least 2 (preferably 2) nitrogen atoms (preferably a 5-membered aromatic heterocyclic group) And a group represented by the general formula (L) are particularly preferable.

X may be a photographically useful group. Examples of the photographically useful group include development inhibitors, desilvering accelerators, redox compounds, dyes, couplers, and the like, or precursors thereof.
In the present invention, it is preferably not a photographic useful group as described above.

  In order to immobilize the coupler in the light-sensitive material, it is preferable that at least one of Q, R 1, X, or R 2 has a total carbon number including a substituent of 8 or more and 50 or less, more preferably the total carbon number Is 10 or more and 40 or less.

Among the compounds represented by the general formula (Y), a preferable compound can be represented by the following general formula (II). Hereinafter, the compound represented by formula (II) will be described in detail.

  In the general formula (II), R1, R2, m and X represent the same as those described in the general formula (Y), and preferred ranges are also the same.

In general formula (II), R3 represents a substituent. Examples of this substituent include those listed as examples of the substituent for R1 described above. Preferably, R3 is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl, isopropyl), aryl group (eg, phenyl, naphthyl), alkoxy group (eg, methoxy, isopropyloxy), aryloxy group (Eg phenoxy), acyloxy group (eg acetyloxy), amino group (eg dimethylamino, morpholino), acylamino group (eg acetamido), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (eg methoxy Carbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), carbamoyl group (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-methyl) Rufamoiru, N, N-diethyl-sulfamoyl), an alkylsulfonyl group (e.g. methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), a cyano group, a carboxyl group, a sulfo group.
n represents an integer of 0 or more and 4 or less. When n is 2 or more, the plurality of R3 may be the same or different from each other, and may be bonded to each other to form a ring.

Of the couplers represented by formula (Y) or formula (II) in the present invention, preferred specific examples are shown below, but the present invention is not limited thereto.
The hydrogen atom at the coupling position (hydrogen atom on the carbon atom substituted by X) is the nitrogen atom of the C = N part bonded to the coupling position (the nitrogen atom constituting the ring and not bonded to R1). ) Tautomers moved up are also included in the present invention.

  The dye-forming coupler represented by the general formula (Y) can be easily synthesized by a method described in JP-A-2003-173007 or a method according to the method described.

Dye-forming coupler represented by the general formula (Y), the silver halide photographic light-sensitive material of the present invention, it is preferable to add 1 × 10 ^-3 to 1 mol per mol of silver halide, 2 × 10 ^-3 It is more preferable to add ˜3 × 10 ⁻¹ mol.
More preferable range of the coating amount of the dye-forming coupler represented by the general formula (Y) is specifically 0.1 mmol / m ² or more and 0.7 mmol in the silver halide photographic light-sensitive material of the present invention. / M ² or less is preferable, 0.2 mmol / m ² or more and 0.6 mmol / m ² or less is more preferable, and 0.3 mmol / m ² or more and 0.5 mmol / m ² or less is most preferable.

  As the magenta coupler used in the present invention, 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly-known literature in Table 1 described later are used. Among them, hue, image stability, color development, and the like are used. A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly connected to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245 in view of properties, etc. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-65246, and pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254 And European Patent Nos. 226849A and 294785A in the sixth place. Use of pyrazoloazole couplers having an alkoxy group or an aryloxy group. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984, and paragraph numbers 0009 to 0026 of the publication are directly applied to the present invention. It is incorporated as part of this specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in the specifications of European Patent Nos. 854384 and 844640 are also preferably used.

  The light-sensitive material of the present invention is preferably color-developed with a color developing composition containing a color developing agent to form a dye image. Preferred examples of the color developing agent include known aromatic primary amine compounds (aromatic primary amine color developing agents), particularly p-phenylenediamine derivatives, and examples are shown below.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide

Of the above p-phenylenediamine derivatives, exemplary compounds 5), 6), 7), 8) and 12) are particularly preferable. Among them, compounds 5) and 8) are preferable, and compound 8) absorbs after dye formation. And most preferable from the viewpoint of image storage stability. Moreover, these p-phenylenediamine derivatives are usually in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate in the state of a solid material.
The content of the aromatic primary amine developing agent in the processing agent is such that the concentration of the developing agent in the working solution is from 2 mmol to 200 mmol, preferably from 6 mmol to 100 mmol, more preferably from 10 mmol to 1 L of the developing solution. It is added to 40 mmol.

Below, the compound represented by general formula (I) is demonstrated in detail.
In the general formula (I), R ^{21 to} R ²⁹ represent a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, Carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl Group, phosphonyl group, aryloxy group Examples thereof include a sulfonyl group and an acyl group. These groups may be further substituted with a substituent as exemplified for R ²¹ . However, at least one of R ^{21 to} R ²⁹ is a substituent.

In the general formula (I), R ^{21 to} R ²⁹ are more specifically a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an aliphatic group (for example, a linear or branched chain having 1 to 32 carbon atoms). Alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-penta) Decylphenoxy) propyl, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamido} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4 -Di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl) Enyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano Group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2- Methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (eg, acetamide, benzamide, tetradecanamide, 2- (2,4-di) -T-amyl phenoki ) Butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino groups (eg methylamino, butylamino, dodecylamino) , Diethylamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanaminoaminolino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2 -Chloro-5- {2- (3-tert-butyl-4-hydroxyphenoxy) dodecanamido} anilino),

A ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), An alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5) -T-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group For example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methy-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) Sulfonyl groups (eg methanesulfur Nyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

An azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy), a carbamoyloxy group (for example, N- Methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy groups (for example, trimethylsilyloxy, dibutylmethylsilyloxy), sulfonyloxy groups (for example, methanesulfonyloxy, octanesulfonyloxy, benzenesulfonyloxy), aryloxycarbonylamino groups ( For example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide, 3-octadecenyl succinimide), heterocyclic thio group (for example, 2-benzothiazolylthio) 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group ( For example, it represents phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl). .

In general formula (I), R ^{21 to} R ²⁹ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, an alkoxy group, an aryloxy group, an acylamino group, an anilino group, or a ureido group. Sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, acyloxy group, carbamoyloxy group, sulfonyloxy group, aryloxycarbonylamino Group, phosphonyl group and aryloxycarbonyl group. R ^{21 to} R ²⁹ are more preferably a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, an aryloxy group, an acylamino group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyl group, or a hydroxy group. R ^{21 to} R ²⁹ are most preferably a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a hydroxy group.

In general formula (I), R ²² is particularly preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 8 or less carbon atoms, and a hydrogen atom or an alkyl group having 4 or less carbon atoms. Is most preferable. The compound represented by formula (I) preferably has an oil-solubilizing group in the molecule, is easily soluble in a high-boiling organic solvent, and is non-diffusible in the hydrophilic colloid layer. From this point, the total carbon number of the compound represented by the general formula (I) is preferably 16 to 60, and more preferably 18 to 50.

In the compound represented by the general formula (I), R ^{21 to} R ²⁹ contain a compound residue represented by the general formula (I) to form a dimer or higher multimer, or a polymer. It may contain a chain to form a homopolymer or copolymer. A typical example of the polymer or copolymer containing a polymer chain is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a compound residue represented by the general formula (I). . In this case, one or more types of repeating units having the compound residue represented by the general formula (I) may be contained in the polymer, and acrylic acid ester, methacrylic acid ester, maleic acid ester as a copolymer component. A copolymer containing one or more of non-color-developing ethylene monomers that do not couple with the oxidation product of an aromatic primary amine developer such as

  Hereinafter, although the specific example (Exemplary compound (I-1)-(I-34)) of a compound represented by general formula (I) is shown, it is not limited to these.

  The compound represented by the general formula (I) can be synthesized by a known method, for example, a method described in International Publication WO00 / 23849 or Japanese Patent Application Laid-Open No. 2000-122243, or a method analogous thereto.

The compound represented by the general formula (I) includes a dye-forming coupler that forms an azomethine dye having a solubility in ethyl acetate of 1 × 10 ⁻⁸ mol / L to 5 × 10 ⁻³ mol / L in the present invention. Although it is used in combination, it may be added to any of the non-photosensitive hydrophilic colloid layers, but it is preferably added to the non-photosensitive hydrophilic colloid layer excluding the uppermost layer. Added to a non-photosensitive hydrophilic colloid layer adjacent to a layer containing a coupler that forms an azomethine dye having a solubility in ethyl acetate of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less. Most preferably.

The addition amount of the compound represented by the general formula (I) is preferably 10 to 400% by mass, and preferably 20 to 300% by mass with respect to the dye-forming coupler that forms the organic solvent sparingly soluble dye of the present invention. The case is further preferred, and the case of 50 to 200% by mass is most preferred.
Two or more compounds represented by the general formula (I) may be used in combination, or may be used in combination with other color mixing inhibitors such as hydroquinones.

  In the silver halide color photographic light-sensitive material of the present invention, various organic and metal complex anti-fading agents can be used in combination in order to further improve the storage stability of the dye image. Examples of organic fading inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Metal complexes include nickel. There are complexes, zinc complexes, etc., cited in Research Disclosure No. 17643, No. VII I to J, No. 15162, No. 18716, left column on page 650, No. 36544, page 527, No. 307105, page 872, and No. 15162. Can be used.

  As the organic anti-fading agent, those described in the following patent publications are preferable. Examples of the aromatic compounds include general formula (I) of JP-B 63-50691, general formulas (IIIa) (IIIb) (IIIc) of JP-B-2-37575, and general formulas of JP-A-2-50457. 5-67220, general formula (IX) of 5-70809, general formula of JP-A-6-19534, general formula (I) of JP-A-62-227889, 62- General formula (I) (II) of 244046 gazette, General formula (I) (II) of JP-A-2-665541, General formula (II) (III) of 2-139544 gazette, 2-196402 General formula (I) of JP-A No. 2-22836, general formulas (B), (C) and (D) of JP-A No. 2-212836, general formula (III) of JP-A No. 3-200758, and general formulas of JP-A 3-48845 (II) (III), 3-266 General formulas (B), (C) and (D) of Japanese Patent No. 36, General formula (I) of Japanese Patent No. 3-969440, General formula (I) of Japanese Patent No. 4-330440, and Japanese Patent No. 5-297541 General formula (I), general formula of JP-A-6-130602, general formula (1) (2) (3) of WO 91/11749, general formula (I) of DE 4,008,785A1, US 4, It is a compound represented by general formula (II) of 931,382, general formula (a) of EP203746B1, and general formula (I) of EP264730B1.

  Examples of the cyclic amine compound include general formula (I) of JP-B-2-32298, general formula (I) of JP-A-3-39296, general formula of JP-A-3-40373, and JP-A-2-49762. General formula (I) in the publication, general formula (II) in the publication 2-208653, general formula (III) in the publication 2-217845, general formula (B) in US Pat. No. 4,906,555, EP309400A2 It is a compound represented by the general formula of the publication, the general formula of the publication 309401A1, the general formula of the publication 309402A1, and the like.

  Examples of amine compounds include general formula (I) of JP-B-6-97332, general formula (I) of JP-B-6-97334, general formula (I) of JP-A-2-148037, General formula (I) of the -150841 gazette, General formula (I) of the gazette 2-181145, General formula (I) of the gazette 3-266636, General formula (IV) of the gazette 4-350854, It is a compound represented by general formula (I) and the like in JP-A-5-61166. Examples of the thioether compound include general formula (I) of JP-B-2-44052, general formula (T) of JP-A-3-48242, general formula (A) of JP-A-3-266636, and 5-323545. It is a compound represented by general formula (I) (II) (III) of the gazette, general formula (I) of JP-A-6-148837, general formula (I) of US Pat. No. 4,933,271, and the like. Examples of the phosphorus compound include general formula (I) in JP-A-3-25437, general formula (I) in JP-A-3-142444, general formula in US Pat. No. 4,749,645, and 4,980,275. The compound represented by the general formula etc. of No. gazette is included.

  In addition to these compounds, general formula (I) of alkene compounds in US Pat. No. 4,713,317, general formula (I) of Japanese Unexamined Patent Publication No. 4-174430 for boron compounds, and US Pat. No. 5,183,731 of epoxy compounds. General formula (II) of the publication, general formula (S1) of JP-A-8-53431, general formula of EP271322B1 of disulfide compounds, general formula (I) (II) (III) of JP-A-4-19736 (IV), general formula (1) of US Pat. No. 4,770,987 of sulfinic acid compounds, general formula (I) (II) (III) (IV) of US Pat. No. 5,242,785 of reactive compounds, A compound represented by the general formula (1) of JP-A-8-283279 as a cyclic phosphorus compound is also effective.

  Metal complexes are also effective, and many are known and effective, such as dithiolate-type nickel complexes and salicylaldoxime-type nickel complexes. However, the general formula (I) of JP-B-61-13736 and JP-B-61- General formula (I) of Japanese Patent Publication No. 13737, General formula (I) of Japanese Patent Publication No. 61-13738, General Formula (I) of Japanese Patent Publication No. 61-13739, and General Formula (I) of Japanese Patent Publication No. 61-13740 ), General formula (I) of Japanese Patent Publication No. 61-13742, general formula (I) of Japanese Patent Publication No. 61-13743, general formula (I) of Japanese Patent Publication No. 61-13744, and Japanese Patent Publication No. 5-69212 JP-A-5-88809, general formula (I) (II), JP-A-63-199248, general formula (I) (II), JP-A-64-75568, general formula (I) (II), Kaihei 3-18274 General formulas (I) and (II) described in US Pat. No. 4,590,153, general formulas (II), (III), (IV) and (V) described in US Pat. No. 4,590,153, and general formulas described in US Pat. II) (III) (IV) and the like are more effective.

Hereinafter, a silver halide color photosensitive material (hereinafter referred to as a photosensitive material) applied to the image forming method of the present invention will be described.
The light-sensitive material is a photosensitive silver halide emulsion layer containing a yellow dye-forming coupler, a light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, a light-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, and a non-photosensitive material. It has a photographic composition layer comprising at least one photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is used as a yellow coloring layer (Y), the silver halide emulsion layer containing the magenta dye-forming coupler is used as a magenta coloring layer (M), and the cyan dye-forming coupler. The silver halide emulsion layer containing the silver functions as a cyan coloring layer (C).
The silver halide emulsions contained in the Y, M, and C color-developing layers are respectively adapted to light in three different wavelength regions (for example, blue, green, and red light in the order of Y, M, and C). On the other hand, it is preferable to have photosensitivity.

  For the above photosensitivity, the three different spectral sensitivities can be arbitrarily selected from the use of a digital exposure method using a semiconductor laser or LED as a light source. At this time, from the viewpoint of color separation, it is preferable that the nearest spectral sensitivity maximum is separated by at least 30 nm or more. The correspondence relationship with the color couplers (Y, M, C) contained in the photosensitive layers (λ1, λ2, λ3) having at least three different spectral sensitivity maxima can be arbitrarily combined. Furthermore, it is also possible to use wavelength ranges other than blue, green, and red light, and it is also preferable that the infrared spectral sensitivity can be accommodated.

  In addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, the photosensitive material may have an antihalation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer to be described later if desired.

The silver halide emulsion will be described.
The grain shape of the silver halide emulsion is not particularly limited, but is substantially a cubic or tetradecahedral crystal grain having {100} faces (these grains have round vertices and higher order faces). It is preferable that the crystal grains are octahedral, and the main surface is composed of tabular grains having an aspect ratio of 2 or more, which are {100} faces or {111} faces. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle.
In the present invention, cubic or tetrahedral particles are more preferable.

The silver halide emulsion contains silver chloride, and the silver chloride content is preferably 90 mol% or more. From the viewpoint of rapid processability, the silver chloride content is more preferably 93 mol% or more. Preferably, 95 mol% or more is more preferable.
The silver halide emulsion preferably contains silver bromide and / or silver iodide. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and excellent in latent image stability.
The silver iodide content is preferably 0.02 to 1 mol%, more preferably 0.05 to 0.50 mol%, more preferably 0.07 to 0.40 mol% is most preferred.
The silver halide emulsion is preferably a silver iodobromochloride emulsion, and more preferably a silver iodobromochloride emulsion having the above-described halogen composition.

  The silver halide emulsion preferably has a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of the minimum It is necessary to have one contained phase, preferably at least one contained phase each.

  The silver bromide-containing phase or silver iodide-containing phase of the silver halide emulsion is preferably layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In that case, the silver bromide-containing phase and the silver iodide-containing phase may be in the same place or in different places of the grain, but it is easier to control grain formation if they are in different places. preferable. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  The silver bromide content or silver iodide content of the silver halide emulsion increases as the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain, and the silver chloride content is reduced more than necessary. This may impair the rapid processability. Therefore, it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic action near the surface in the grain. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  In order to incorporate silver bromide or silver iodide into a silver halide emulsion, bromide or iodide ions can be introduced by adding a bromide salt or an iodide salt solution alone, or by adding a silver salt solution and a high chloride salt. Along with the addition of the solution, a bromide salt or iodide salt solution may be added. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  The variation coefficient of the equivalent sphere diameter of all the grains contained in the silver halide emulsion is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating. Here, in this specification, the sphere equivalent diameter of a particle is represented by the diameter of a sphere having a volume equal to the volume of each particle. The silver halide emulsion is preferably composed of grains having a monodispersed grain size distribution.

  The equivalent sphere diameter of the grains contained in the silver halide emulsion is preferably 0.6 μm or less, preferably 0.5 μm or less, and more preferably 0.4 μm or less. The lower limit of the equivalent sphere diameter of the silver halide grains is preferably 0.05 μm, more preferably 0.1 μm. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.4 μm, and a sphere equivalent diameter of 0. A 4 μm particle corresponds to a cubic particle having a side length of about 0.32 μm.

  The silver halide emulsion preferably contains iridium. Iridium preferably forms an iridium complex, and a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is preferable, and all six ligands are composed of Cl, Br, or I. More preferred is a hexacoordinate complex having a central metal. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex containing Ir as a central metal having Cl, Br or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

Specific examples of hexacoordination complexes having Ir as a central metal, in which all six ligands are Cl, Br, or I, include [IrCl ₆ ] ²⁻ , [IrCl ₆ ] ³⁻ , [IrBr ₆ ] ²⁻ , Examples include [IrBr ₆ ] ³⁻ and [IrI ₆ ] ³⁻ , but are not limited thereto.

As another preferred embodiment of iridium, a hexacoordination complex having at least one ligand other than halogen and cyan as a central metal is preferable, and H ₂ O, OH, O, OCN, thiazole or substituted thiazole, thiadiazole or Preferred is a hexacoordination complex having Ir as a central metal having a substituted thiadiazole as a ligand, and at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligands being Cl, Br or A hexacoordinate complex having Ir as the central metal is more preferable. Furthermore, one or two 5-methylthiazole, 2-chloro-5 fluorothiadiazole or 2-bromo-5 fluorothiadiazole is used as a ligand, and the remaining ligand is Cl, Br or I. Hexacoordination complexes are most preferred.

Specific examples of hexacoordination complexes having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand is Cl, Br or I and having Ir as a central metal include: _{[Ir (H 2 O) Cl} 5] 2-, [Ir (OH) Br 5] 3-, [Ir (OCN) Cl 5] 3-, [Ir ( ^{_{thiazole) Cl 5] 2-, [Ir}} (5 - ^{_{methylthiazole) Cl 5] 2-, [Ir}} (2- chloro-5-fluorothiazole thiadiazole) Cl _5] ^2- and [[Ir (2-bromo-5-fluorothiazole thiadiazole) Cl _5] include ^2- but, It is not limited to these.

In addition to the above iridium complexes, the silver halide emulsion is [Fe (CN) ₆ ] ⁴⁻ , [Fe (CN) ₆ ] ³⁻ , [Ru (CN) ₆ ] ⁴⁻ , [Re (CN) ₆ ] ^{4. -} , [Os (CN) ₆ ] It is preferable to contain a hexacoordination complex having a CN ligand such as ^4-, Fe, Ru, Re, or Os as a central metal. The silver halide emulsion used in the present invention further has a pentachloronitrosyl complex, a pentachlorothionitrosyl complex having Ru, Re or Os as a central metal, or Rh having Cl, Br or I as a ligand as a central metal. It is preferable to contain a coordination complex. These ligands may be partially aquaated.

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. The optimum amount of these metal complexes varies depending on the type, but it is preferable to add 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and 1 × 10 ⁻⁹ mol to 1 × It is most preferable to add 10 ⁻⁵ mol.

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

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

  Silver halide emulsions are usually chemically sensitized. As the chemical sensitization method, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced.

  For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

  Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as bis (1,4,5-trimethyl-1, 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate, organomercaptogold (I) complexes described in JP-A-11-218870, for example, potassium bis (1- [3- (2-sulfonate benzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) orate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan Toinert) gold (I) sodium salt tetrahydrate can be used. The gold (I) compound having these organic ligands may be synthesized in advance and isolated, or may be mixed with an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof). Can be added to the emulsion without generation and isolation. Furthermore, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) may be added separately to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.

Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, The compounds described in Japanese Patent Nos. 5620841, 5912112, 5620841, 5939245, and 5912111 can also be used. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, per mol of silver halide. is there.

Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics Vol. 79, 60-66, 1995, Compt. Rend. Hebt. Seans Acad. Sci. Sect. B 263, 1328, 1966, etc. The amount of colloidal gold sulfide may vary widely depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻ as gold atoms per mol of silver halide. ⁴ moles.

In addition to gold sensitization, chalcogen sensitization can be performed with the same molecule, and a molecule capable of releasing AuCh- can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. Examples of the amount capable of releasing AuCh- include gold compounds represented by AuCh-L. Here, L represents an atomic group constituting a molecule by binding to AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. Specific examples of compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, and gold thioarabinose), selenosugar Au (I) salts (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurose, and the like.
Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, or a TeH group, respectively. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol, per mol of silver halide. is there.

  The silver halide emulsion may be combined with the above gold sensitization and other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using other than gold compounds. Good. It is particularly preferable to combine with sulfur sensitization and selenium sensitization.

  Various compounds or precursors thereof can be added to the silver halide emulsion for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.

  In order to increase the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576, the carbonyl group described in JP-A-11-327094, and both ends are amino groups or Cyclic ketones having a double bond substituted with a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated herein), JP-A-11-143011 Sulfo-substituted catechols and hydroquinones described in the publication (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfone) 1,2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5- Rehydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (see US Pat. No. 5,556,741). The description in line 4 line 56 to column 11 line 22 is also preferably applied in the present invention, and is incorporated as part of this specification), and general formula (I)- The water-soluble reducing agent represented by (III) is also preferably used in the present invention.

The silver halide emulsion may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity that exhibits photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for partial sensitization in the blue, green, and red regions include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & ons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.
Also in the application of the digital exposure method, the spectral sensitization is performed for the purpose of imparting an arbitrary spectral sensitivity according to the light wavelength range of the light source, and it is also preferable to have an infrared spectral sensitization if necessary. As the spectral sensitization method for digital exposure, the method described in JP-A-5-142712 is also preferable, and the compound described in the same publication is preferably used as the infrared spectral sensitizing dye.

The amount of these spectral sensitizing dyes to be added varies widely depending on the case, and is preferably in the range of 0.5 × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol per mol of silver halide. More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol.

  Hereinafter, the photosensitive material of the present invention will be described in more detail.

  Gelatin is used as a hydrophilic binder in the light-sensitive material, but other gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, mono- or copolymer as necessary. Hydrophilic colloids such as synthetic hydrophilic polymer materials can also be used in combination with gelatin. The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be either lime-processed gelatin or acid-processed gelatin, or may be gelatin manufactured using any raw material such as cow bone, cow skin, or pig skin. Preferred is lime-processed gelatin made from beef bone and pig skin.

As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

The total coating amount of gelatin in the photographic composition layer in the light-sensitive material is, i.e., the photosensitive silver halide emulsion layer from the support to the hydrophilic colloid layer farthest from the support on the side where the silver halide emulsion layer is coated. The total amount of the hydrophilic binder contained in the non-photosensitive hydrophilic colloid layer is preferably 4.0 g / m ² or more and 7.0 g / m ² or less, more preferably 4.0 g / m ² or more and 6.5 g. / M ² or less, most preferably 4.5 g / m ² or more and 6.0 g / m ² or less. When the amount of the hydrophilic binder is larger than the above range, the effect of the present invention is reduced by impairing the rapidity of color development processing, deteriorating the Brix fading, and impairing the rapid processability of the rinsing process (washing and / or stabilizing process). May decrease. In addition, when the amount of the hydrophilic binder is less than the above range, it is not preferable because it is liable to cause harmful effects due to insufficient film strength such as pressure covering stripes.

  The photosensitive material can be decolorized by processing as described in pages 27 to 76 of EP 0337490A2 in the hydrophilic colloid layer for the purpose of preventing irradiation and halation, and improving safetylight safety. It is preferable to add various dyes (especially oxonol dyes and cyanine dyes). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As the dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  For the light-sensitive material, a colored layer that can be decolored by processing in combination with a water-soluble dye or in combination with a water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to individually install all the colored layers corresponding to each primary color, or to select and install only some of them. It is also possible to install colored layers corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength with the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  In order to form the colored layer, a conventionally known method can be applied. For example, solid dye dispersions such as dyes described in JP-A-2-282244, page 3, upper right column to page 8, and dyes described in JP-A-3-7931, page 3, upper right column to page 11, lower left column. Described in JP-A-1-239544, a method of incorporating a hydrophilic colloid layer in a state, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer Such as using colloidal silver. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. 2-308244, pages 4-13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show methods for preparing colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  The light-sensitive material preferably has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. The silver halide emulsion layer is a yellow color-developing silver halide emulsion layer, a magenta color-developing silver halide emulsion layer, and a cyan color-developing silver halide emulsion layer in order from the support.

However, a different layer structure may be used.
In the light-sensitive material, the silver halide emulsion contained in the blue-sensitive silver halide emulsion layer is a green-sensitive silver halide emulsion or a red-sensitive material because of the spectral characteristics of the negative yellow mask and the halogen used as the light source during exposure. It is preferable that the sensitivity is relatively high with respect to the silver halide emulsion. Therefore, the grain side length of the blue-sensitive emulsion is preferably larger than the grain side length of the other layer. Furthermore, the molar extinction coefficient of a generally known yellow coupler coloring dye is lower than that of a magenta coupler coloring dye or a cyan coupler coloring dye, and the amount of blue-sensitive emulsion coating increases as the yellow coupler coating amount increases. There is a tendency. For this reason, the yellow-colored blue-sensitive silver halide emulsion layer is disadvantageous compared to other layers in consideration of resistance to pressure from the surface of the photosensitive material, such as scratching, and is preferably located on the side closer to the support. .

  That is, the silver halide emulsion layer containing the yellow coupler may be disposed at any position on the support, but when the silver halide emulsion layer contains silver halide tabular grains, it contains a magenta coupler. It is preferably coated at a position farther from the support than at least one silver halide emulsion layer or cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of color development acceleration, desilvering acceleration, and reduction of residual color by sensitizing dye, the yellow coupler-containing blue-sensitive silver halide emulsion layer is positioned farthest from the support than other silver halide emulsion layers. It is preferable to be coated. Further, from the viewpoint of reducing photobleaching, the cyan coupler-containing silver halide emulsion layer is preferably the lowermost layer or the middle layer of the emulsion layer. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers.

  Examples of silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied to the photosensitive material, and processing methods and processing additives applied to process this photosensitive material JP-A-62-215272, JP-A-2-33144, and those described in European Patent EP0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854. The silver halide color photographic light-sensitive materials and the processing methods thereof described in JP-A Nos. 1-158431, 2-90145, 3-194539, 2-93641, and European Patent Publication No. 0520457A2 are also preferable.

  In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), gelatin type, layer structure of the photosensitive material, coating film pH of the photosensitive material, and the like, those described in each part of the patent documents shown in the following table can be particularly preferably applied.

In the light-sensitive material of the present invention, the dye-forming coupler is preferably emulsified and dispersed together with a photographically useful substance and other high-boiling organic solvents, and incorporated into the light-sensitive material as a dispersion. This liquid is emulsified and dispersed in a fine particle form in a hydrophilic colloid, preferably an aqueous gelatin solution, together with a surfactant dispersing agent, using a known apparatus such as ultrasonic wave, colloid mill, homogenizer, manton gourin, high-speed dissolver, etc. Get.
The high-boiling organic solvent is not particularly limited, and ordinary ones are used, and examples thereof include those described in US Pat. No. 2,322,027 and JP-A-7-152129.
An auxiliary solvent can be used together with the high boiling point organic solvent. Examples of cosolvents include acetates of lower alcohols such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, s-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate and cyclohexanone. Etc.

Further, if necessary, an organic solvent that is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide and the like can be used in combination. Moreover, these organic solvents can also be used in combination of 2 or more types.
From the viewpoint of improving stability over time during storage in the emulsion dispersion state, suppressing photographic performance changes in the final coating composition mixed with emulsion, and improving stability over time, the emulsion dispersion may be reduced in pressure as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation, washing with noodles or ultrafiltration.
The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, most preferably 0.06 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (Coulter Electronics, trade name) or the like.

  In addition, a tinting pigment may be co-emulsified in the emulsion used in the present invention to adjust the color of a white background, and an organic solvent that dissolves a photographic useful compound such as a coupler used in the photosensitive material of the present invention. It may be co-emulsified and co-emulsified to prepare an emulsion.

The cyan, magenta and yellow couplers used in the light-sensitive material have already been described. In addition, JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6 JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and EP 0355660 A2. Couplers described on page 4, line 15 to line 27, page 5, line 30 to page 28, line 45, page 29, line 31 to line 31, page 47, line 23 to page 63, line 50 are also useful. is there.
In the present invention, compounds represented by general formulas (II) and (III) of WO 98/33760 and general formula (D) of JP-A-10-221825 may be added, which is preferable.

  Couplers that can be used in the light-sensitive material are impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence (or absence) of the high-boiling organic solvent described in the above table. Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.

For the light-sensitive material, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber. For example, compounds described in the following patent documents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive.
For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, JP-A-8-53427, and 8- No. 234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. The compounds described in No. -502911, etc. can be used.

  An antibacterial / antifungal agent as described in JP-A-63-271247 is added to the photosensitive material in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

A surfactant can be added to the photosensitive material from the standpoints of improving coating stability, preventing static electricity generation, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The photosensitive material is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper.
As the photographic support that can be used for the photosensitive material, a transmissive support or a reflective support can be used. As a transmissive support, a permeable film such as a cellulose triacetate film or polyethylene terephthalate, a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), or a polyester of NDCA, terephthalic acid and EG, etc. Those provided with an information recording layer such as a magnetic layer are preferably used.
In the present invention, a reflective support is preferred, and in particular, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one layer of such a water-resistant resin layer (laminate layer). Is preferred.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. The fluorescent brightening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based optical brighteners are more preferable. Specific examples of the optical brightener contained in the water-resistant resin layer include 4,4′-bis (benzoxazolyl) stilbene and 4,4′-bis (5-methylbenzoxazolyl) stilbene. And a mixture thereof. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.

  The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular reflective or second-type diffuse reflective metallic surface.

  More preferable examples of the reflective support include those having a polyolefin layer having fine pores on the paper substrate on the side where the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg polypropylene, polyethylene) and is close to the paper substrate More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.7 g / ml. The thickness of the multilayer or single polyolefin layer located between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

  In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are described in JP-A Nos. 10-333277, 10-333278, 11-52513, 11-65024, EP0880065, and Examples are described in EP 0880066.

  The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) that combines a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds. It is as follows.

  The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. A recording system including a color image recording system described in JP-A-11-88619 and JP-A-10-202950, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, And a photo print system including the image recording apparatus described in JP 2000-310822 A.

  The preferred scanning exposure method applicable to the present invention is described in detail in the publications listed in Table 1 above.

When the light-sensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility.
In the present invention, as described in European Patent Nos. EP0789270A1 and EP0789480A1, a yellow microdot pattern may be pre-exposed in advance and copy control may be performed before image information is added.

  In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 The processing materials and processing methods described in the 20th page, lower right column, line 20 are preferably applicable. As the preservative used in the developer, compounds described in the patent documents listed in the above table are preferably used.

The present invention is preferably applied to a light-sensitive material having rapid processing suitability. In the case of rapid processing, the color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, more preferably 30 seconds or less and 6 seconds or more, and most preferably 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, more preferably 30 seconds or less and 6 seconds or more, and most preferably 20 seconds or less and 6 seconds or more. Further, the washing time or stabilization time is preferably 150 seconds or shorter, more preferably 130 seconds or shorter and 6 seconds or longer.
The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer and are bleached in the next processing step. The sum of both the time during which the toner is conveyed in the air toward the fixing bath (so-called air time) is referred to as color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Acetic acid in a mixture of 4.1 g of exemplary compound CP- (1), 3.53 g of 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline and 2.8 g of anhydrous sodium carbonate 20 ml of ethyl, 20 ml of ethanol and 10 ml of water were sequentially added and stirred at room temperature. An aqueous solution in which 3.62 g of ammonium persulfate was dissolved in 20 ml of water was dropped into this mixture. After completion of the dropwise addition, stirring was continued for 2 hours at room temperature, and the precipitated crystals were collected by filtration and washed successively with water and ethanol. The crystals were dried and recrystallized from methanol to obtain 3.45 g (yield 70%) of the intended (Dye 1) as purple crystals. The structure of the obtained compound was confirmed by ¹ HNMR and mass spectrum.

¹ HNMR (300 MHz, DMSO-d ₆ ) δ 0.90 (18H, s), 1.09 (3H, d), 1.25 (3H, t), 1.28 (9H, s), 1.3 to 1.8 (7H, m), 2.98 (3H, s), 3.25 (2H, m), 3.36 (3H, s), 3.72 (4H, m), 3.96 (3H) , S), 6.00 (1H, s), 7.00 (2H, m), 7.20 (1H, d), 7.30 (1H, t), 7.95 (1H, d), 8 .54 (1H, s), 8.70 (1H, s), 9.16 (1H, br.s)
MS m / z 856 (M +)
Melting point: 276-279 ° C
Λmax = 634 nm in ethyl acetate εmax = 5.9 × 10 ⁴ cm ⁻¹ M ⁻¹

50 mg of (Dye 1) was added to 20 ml of ethyl acetate and dissolved by ultrasonic stirring to prepare a supersaturated dispersion at 25 ° C. The spectral absorption spectrum (1 mm quartz glass cell) was measured for the dye saturated solution obtained from the filtrate of this supersaturated solution. From the measured absorbance at the maximum absorption wavelength, the solubility of (Dye 1) was 5.5 × 10 ⁻⁴ mol / L.

(Dye 2), (Dye 3), (Dye) using Exemplified Compounds CP- (2), CP- (5), and the coupler (ExC-1) described in Example 2 in the same manner as above 4) was synthesized, and the solubility of each dye was further determined. The results are shown in Table 2.

As is apparent from the results in Table 2, the azomethine dyes (dyes 1 to 3) formed from the cyan coupler represented by the general formula (CP-I) used in the present invention have a solubility in ethyl acetate of 1 ×. It was in the range of 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less.

(Preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by a method in which a silver nitrate solution and a sodium chloride solution were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from the time when the addition of silver nitrate was 10% to 20%. From 70% to 85% addition of silver nitrate, potassium bromide (3.0 mole% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₆ ] was added from 75% to 80% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from the time when the addition of silver nitrate was 88% to 98%. When the addition of silver nitrate was completed 93%, potassium iodide (0.3 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.25 μm and a coefficient of variation of 9.5%. The emulsion was subjected to precipitation desalting treatment, and gelatin, compounds (Ab-1), (Ab-2), (Ab-3), and calcium nitrate were added thereto and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, SE-1 as a selenium sensitizer, and (bis (1,4,5-trimethyl-1,2 as a gold sensitizer). , 4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, repeating unit 2 or 3 represented by 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3 is a main component. (Terminal X ₁ and X ₂ are hydroxyl groups), compound-4 and potassium bromide were added. Further, spectral sensitization was performed by adding sensitizing dyes S-1, S-2, and S-3 during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
Emulsion grains were obtained in the same manner as in the preparation of Emulsion BH-1, except that the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.25 μm and a coefficient of variation of 9.5%. After redispersion of this emulsion, emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of emulsion BH-1 to obtain the desired sensitivity.

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 70% to 85% addition of silver nitrate. Potassium bromide (1 mole% per mole of finished silver halide) was added from 70% to 85% addition of silver nitrate. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 70% to 85% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from the time when the addition of silver nitrate was 87% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.25 μm and a coefficient of variation of 9.5%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C., sodium benzenethiosulfate, p-glutaramide phenyl disulfide, SE-1 as a selenium sensitizer and (bis (1,4,5-trimethyl-1,2,4) as a gold sensitizer. -Triazolium-3-thiolate) orate (I) tetrafluoroborate) was added and aged for optimal chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of green-sensitive layer emulsion GL-1)
Emulsion grains were obtained in the same manner as in the preparation of Emulsion GH-1, except that the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.25 μm and a coefficient of variation of 9.5%. After redispersion of this emulsion, emulsion GL-1 was prepared in the same manner as emulsion GH-1, except that the amount of chemical sensitizer added was changed from that of emulsion GH-1 to obtain the desired sensitivity.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from 93% to 98% addition of silver nitrate. Potassium bromide (3 mole percent per mole of finished silver halide) was added from the 85 percent to 100 percent addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 88% to 93% when silver nitrate was added. When 93% of the addition of silver nitrate was completed, potassium iodide (amount of silver iodide to be 0.1 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from the time when the addition of silver nitrate was 93% to 98%. The resulting emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.25 μm and a coefficient of variation of 9.5%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C., and sensitizing dye S-8, compound-5, sodium benzenethiosulfate, p-glutaramide phenyl disulfide, compound-1 as a gold sulfur sensitizer, SE-1 as a selenium sensitizer, and Add (bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) as a gold sensitizer and mature for optimal chemical sensitization did. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(Preparation of emulsion RL-1 for red-sensitive layer)
Emulsion grains were obtained in the same manner as in the preparation of Emulsion RH-1, except that the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.25 μm and a coefficient of variation of 9.5%. After redispersion of this emulsion, Emulsion RL-1 was similarly prepared except that the amount of various compounds added was changed from that of Emulsion RH-1 to obtain the desired sensitivity.

Preparation of first layer coating solution 24 g of yellow coupler (Ex-Y), 6 g of color image stabilizer (Cpd-8), 1 g of color image stabilizer (Cpd-16), 1 g of color image stabilizer (Cpd-17), color image 11 g of stabilizer (Cpd-18), 1 g of color image stabilizer (Cpd-19), 11 g of color image stabilizer (Cpd-21), 1 g of color image stabilizer (UV-A) 17 g of solvent (Solv-4), Dissolve in 3 g of solvent (Solv-6), 17 g of solvent (Solv-9) and 45 ml of ethyl acetate, and dissolve the solution in 205 g of 20% by weight gelatin aqueous solution containing 3 g of sodium dodecylbenzenesulfonate (dissolver). Emulsified and dispersed, and 700 g of emulsified dispersion A was prepared by adding water.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. (H-1), (H-2), and (H-3) were used as gelatin hardeners for each layer. Moreover, (Ab-1), (Ab-2), (Ab-3), and (Ab-4) were added to each layer in a total amount of 10.0 mg / m ² , 43.0 mg / m ² , 3.5 mg / was added such that the m ² and 7.0 mg / m ^2.

1- (3-methyl) -5-mercaptotetrazole, the third layer, fifth layer, and sixth layer, respectively ^{0.2mg / m 2, 0.2mg / m} 2, 0.6mg / m 2 It added so that it might become. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 ×, respectively, per mol of silver halide. 10 ^-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000-400000) was added to the red sensitive emulsion layer. Third layer, was added the fifth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support: Polyethylene resin laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass)), and bluish dye (ultraviolet, content 0.33% by mass). The amount of polyethylene resin is 29.2 g / m ² )]
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.13
Gelatin 1.00
Yellow coupler (Ex-Y) 0.24
Color image stabilizer (Cpd-8) 0.06
Color image stabilizer (Cpd-16) 0.01
Color image stabilizer (Cpd-17) 0.01
Color image stabilizer (Cpd-18) 0.11
Color image stabilizer (Cpd-19) 0.01
Color image stabilizer (Cpd-21) 0.11
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.17
Solvent (Solv-6) 0.03
Solvent (Solv-9) 0.17

Second layer (intermediate coloring layer)
Gelatin 0.33
Yellow coupler (Ex-Y) 0.08
Color image stabilizer (Cpd-8) 0.02
Color image stabilizer (Cpd-16) 0.01
Color image stabilizer (Cpd-17) 0.01
Color image stabilizer (Cpd-18) 0.03
Color image stabilizer (Cpd-19) 0.01
Color image stabilizer (Cpd-21) 0.03
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.05
Solvent (Solv-6) 0.01
Solvent (Solv-9) 0.05

Third layer (color mixing prevention layer)
Gelatin 0.31
Color mixing inhibitor (Cpd-4) 0.024
Color image stabilizer (Cpd-5) 0.004
Color image stabilizer (Cpd-6) 0.020
Solvent (Solv-5) 0.028

Fourth layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.09
Gelatin 0.77
Cyan coupler (ExC-1) 0.16
Cyan coupler (ExC-2) 0.015
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.05
Color image stabilizer (Cpd-16) 0.08
Color image stabilizer (Cpd-17) 0.07
Solvent (Solv-5) 0.15

5th layer (color mixing prevention layer)
Gelatin 0.39
Color mixing inhibitor (Cpd-4) 0.030
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.025
Solvent (Solv-5) 0.035

Sixth layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.09
Gelatin 1.10
Magenta coupler (Ex-M) 0.12
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.005
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-18) 0.01
Ultraviolet absorber (UV-B) 0.26
Solvent (Solv-3) 0.04
Solvent (Solv-4) 0.08
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.12
Solvent (Solv-7) 0.11
Compound (S1-4) 0.0015

Seventh layer (protective layer)
Gelatin 0.44
Additive (Cpd-20) 0.015
Liquid paraffin 0.01
Surfactant (Cpd-13) 0.01

The sample manufactured as described above was designated as Sample 001.
Next, as shown below, the amount of the solvent (Solv-5) was increased with respect to the red photosensitive layer of Sample 001, and the amount of gelatin was increased in proportion to the total amount of the lipophilic component increased. Samples 002 and 003 similar to the sample 001 were prepared except that the amount of the solvent (Solv-5) and the amount of gelatin in the red photosensitive layer were different.

Fourth layer (sample 002 red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.09
Gelatin 1.00
Cyan coupler (ExC-1) 0.16
Cyan coupler (ExC-2) 0.015
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.05
Color image stabilizer (Cpd-16) 0.08
Color image stabilizer (Cpd-17) 0.07
Solvent (Solv-5) 0.30

Fourth layer (red photosensitive emulsion layer of sample 003)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.09
Gelatin 1.26
Cyan coupler (ExC-1) 0.16
Cyan coupler (ExC-2) 0.015
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.05
Color image stabilizer (Cpd-16) 0.08
Color image stabilizer (Cpd-17) 0.07
Solvent (Solv-5) 0.50

  With respect to sample 001, the coupler (ExC-1) of the red light-sensitive emulsion layer was replaced with the exemplified compounds CP- (1), CP- (2), and CP- (5) in equimolar amounts, respectively. As shown in Table 3, the five layers of the color mixing inhibitor (Cpd-4) were replaced with equimolar samples 101 to 104 and 109 to 109, respectively, with the compound represented by the general formula (I) of the present invention. 112 and 114-120 were produced.

In addition, samples 105, 106, and 113 were manufactured for sample 002 in the same manner as described above, and samples 107 and 108 were manufactured for sample 003 in the same manner as described above.
In addition, about the coupler ratio with respect to a total oil-soluble component, it adjusted so that the addition amount of a solvent (Solv-5) may be increased / decreased so that it may become the coupler content shown in Table 3.

  Using the samples 001 to 003 and 101 to 120 prepared as described above, cyan images were obtained by color development described later. As a result of high-performance liquid chromatographic qualitative analysis, the structure of the dye extracted from the cyan image was the dye shown in Table 3 below for the couplers used.

Processing A
The above sample 001 was processed into a 127 mm width roll, and a standard photographic image was exposed using a digital minilab frontier 350 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank. The treatment using this running treatment liquid was designated as treatment A.

Processing process Temperature Time Replenishment color development 38.5 ° C 45 seconds 45 mL
Bleach fixing 38.0 ° C 45 seconds A 17.5mL
B agent 17.5mL
Rinse 1 38.0 ° C. 20 seconds −
Rinse 2 38.0 ° C 20 seconds-
Rinse 3 38.0 ° C. 20 seconds −
Rinse 4 38.0 ° C 20 seconds 121mL
Dry 80 ° C
(note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank counterflow system from 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-1) 2.2g 5.1g
Optical brightener (FL-2) 0.35 g 1.75 g
Triisopropanolamine 8.8g 8.8g
Polyethylene glycol average molecular weight 300 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.20g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate 4.8 g 14.0 g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.15 12.40

[Bleaching Fixer] [Tank Solution] [Replenisher A] [Replenisher B]
Water 800mL 500mL 300mL
Ammonium thiosulfate (750 g / L) 107 mL-386 mL
Ammonium bisulfite (65%) 30.0g-190g
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0 g 133 g −
Ethylenediaminetetraacetic acid 1.4g 5g 6g
Nitric acid (67%) 16.5 g 66.0 g −
Imidazole 14.6 g 50.0 g −
m-carboxybenzenesulfinic acid 8.3 g 33.0 g −
Add water to total volume 1000mL 1000mL 1000mL
pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.5 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

Process B
The sample 001 was processed into a 127 mm width roll, and a standard photographic image was exposed using a digital minilab frontier 340 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank. In addition, the processor changed the conveyance speed by modifying the processing rack in order to make the following processing time. The treatment using this running treatment liquid was designated as treatment B.

Processing process Temperature Time Replenishment amount Color development 45.0 ℃ 12 seconds 35mL
Bleach fixing 40.0 ° C 12 seconds A agent 15mL
B agent 15mL
Rinse 1 45.0 ° C. 4 seconds −
Rinse 2 45.0 ° C. 2 seconds −
Rinse 3 45.0 ° C. 2 seconds −
Rinse 4 45.0 ° C 3 seconds 175 mL
Drying 80 ° C 15 seconds (Note)
* Per photosensitive material 1 m ² replenishment rate

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightening agent (FL-3) 4.0 g 10.0 g
Residual color reducing agent (SR-1) 3.0 g 3.0 g
m-Carboxybenzenesulfinic acid 2.0 g 4.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline 3/2 sulfate monohydride 7.0 g 19.0 g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.8

[Bleaching Fixer] [Tank Solution] [Replenisher A] [Replenisher B]
Water 700mL 300mL 300mL
Ammonium thiosulfate (750 g / L) 107 mL-400 mL
Ammonium sulfite 30.0 g − −
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0g 200g-
Ethylenediaminetetraacetic acid 1.4 g 0.5 g 10.0 g
Nitric acid (67%) 7.0 g 30.0 g −
m-carboxybenzenesulfinic acid 3.0 g 13.0 g −
Ammonium bisulfite solution (65%)--200 g
Succinic acid 7.0 g 30.0 g −
Add water to total volume 1000mL 1000mL 1000mL
pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.0 2.0 5.6

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL
pH (25 ° C.) 6.5 6.5

Samples 001 to 003 and 101 to 120 were subjected to the following evaluation after being applied for 14 days under the condition of 25 ° C. and 55% relative humidity after applying the photosensitive material.
Each sample was subjected to gradation exposure to give gray in the above processing B by the following exposure apparatus, and color development processing was performed in the above processing A and B 5 seconds after the exposure was completed. As a laser light source, a blue laser of about 470 nm and a semiconductor laser (oscillation wavelength of about 1060 nm) extracted by converting the wavelength of a semiconductor laser (oscillation wavelength of about 940 nm) with a LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure are used. A green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG, trade name) extracted by wavelength conversion using a LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by a polygon mirror so that the sample can be sequentially scanned and exposed. The light quantity fluctuation due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. A gray image having a maximum density of 2.3 to 2.5 was obtained from each sample.

(Evaluation of color reproducibility)
Each sample was subjected to R exposure in a gradation manner by the above exposure method, and each cyan gradation image was produced by the treatment A and the treatment B. From the result of the reflection spectrum at a cyan coloring portion density of 1.0, the unnecessary absorption corresponding to magenta or yellow of 550 nm to 400 nm is low and the sensory evaluation is the best (○ is particularly excellent), which is slightly inferior The color reproducibility was evaluated by assuming that the unnecessary absorption corresponding to magenta or yellow of 550 nm to 400 nm was clearly inferior, and x. The samples of the present invention all had a maximum concentration of 2.0 or more.
(Evaluation of light fastness)
The image sample was irradiated with xenon light (100,000 × xenon light irradiator) for 14 days through an ultraviolet cut filter and a heat ray cut filter having a light transmittance of 50% at 370 nm. Light fastness was evaluated by the relative residual ratio (%) after exposure at an initial cyan density of 1.0.
(Evaluation of storage stability on white background)
The suitability for rapid processing of the sample was evaluated based on the temporal stability of the image obtained in Processing B on a white background. The stability of the white background over time was determined by storing the treated sample at 60 ° C. and 70% RH for 21 days, and determining the increase in cyan density before and after storage. The sensory evaluation determined that ΔD was less than 0.05 as a preferred range.
The evaluations of color reproducibility and light fastness are the results of the samples developed in Process B.
The results are shown in Table 4.

The solubility of the azomethine dye obtained from the coupler (ExC-2) in ethyl acetate was 0.5 mol / L or more.
As is apparent from Table 4, the structure of the present invention can provide a color print excellent in color reproducibility, light fastness, and storage stability on a white background in ultra-rapid processing. That is, the red photosensitive layer has a coupler that forms an azomethine dye having a solubility in ethyl acetate of the present invention of 1 × 10 ⁻⁸ mol / L to 5 × 10 ⁻³ mol / L in the lipophilic component. Samples 102 to 106 and 109 to 120 having a coupler content of 18% by mass or more were excellent in any of the above performances. In contrast, Samples 001 to 003 using a comparative coupler had a low color image remaining rate after xenon irradiation, and could not satisfy both color reproducibility and white background preservation at the same time. On the other hand, even if the coupler which forms the azomethine dye whose solubility in ethyl acetate of the present invention is 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less is used, the coupler for the total oil-soluble component The samples (107, 108) having a content of less than 18% by mass and the sample (101) not using the compound represented by the general formula (I) of the present invention were not satisfied with light fastness and storage stability on white background.

Claims (12)

A photosensitive silver halide emulsion layer containing a yellow dye-forming coupler, a photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, a photosensitive silver halide emulsion layer containing a cyan-forming coupler, and a non-photosensitive hydrophilic colloid layer on a support A silver halide color photographic light-sensitive material having at least one layer each having a solubility in ethyl acetate of at least 1 × 10 due to reaction of at least one dye-forming coupler with an oxidized form of an aromatic primary amine compound. A dye-forming coupler that forms an azomethine dye of ^-8 mol / L or more and 5 x 10 ^-3 mol / L or less, wherein the dye-forming coupler is 18 with respect to the total lipophilic component of the layer containing the dye-forming coupler. A compound represented by the following general formula (I) in at least one layer of the non-photosensitive hydrophilic colloid layer: The silver halide color photographic material, wherein at least one is contained in.

In general formula (I), R ^{21 to} R ²⁹ may be the same or different and each represents a hydrogen atom or a substituent. However, at least one of R ^{21 to} R ²⁹ is a substituent. R ^{21 to} R ²⁹ may be a divalent group, and may be combined with a dimer or other monomer or a polymer chain to form a monopolymer or a copolymer. 2. The silver halide color photographic material according to claim 1, wherein the solubility of the azomethine dye in ethyl acetate is 1 × 10 ⁻⁸ mol / L or more and 7 × 10 ⁻⁴ mol / L or less. . The silver halide emulsion layer containing at least one dye-forming coupler for forming the azomethine dye has a total dye-forming coupler coating amount of 0.18 mmol / m ^{2 to} 0.28 mmol / m ² and the dye The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the maximum optical reflection density at the maximum absorption wavelength of the dye after formation is 2.0 or more.   4. The silver halide color photographic light-sensitive material according to claim 1, wherein the maximum absorption wavelength of the azomethine dye is 570 nm to 700 nm. 5. The silver halide color photographic light-sensitive material according to any one of claims 1 to 4, wherein the dye-forming coupler for forming the azomethine dye is a coupler represented by the following general formula (CP-I). material.

In the general formula (CP-I), G _a is -C (R ₂₃₎ = or represents -N =, G _b when G _a represents -N = is -C (R ₂₃₎ = represents, G _a There G _b to represent a -C (R ₂₃₎ = represents -N =. R ₂₁ and R ₂₂ each independently represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more and 1.0 or less. R ₂₃ represents a substituent. Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer. The silver halide color photographic light-sensitive material described above contains at least one selected from dye-forming couplers represented by the following general formula (Y). Silver halide color photographic material.

In General Formula (Y), Q represents a nonmetallic atom group that forms a 5- to 7-membered ring with —N═CN (R1) —. R1 represents a substituent. R2 represents a substituent. m represents an integer of 0 or more and 5 or less. When m is 2 or more, a plurality of R2s may be the same or different from each other, and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.   The oxidized form of the aromatic primary amine compound is an oxidized form of 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline. 7. The silver halide color photographic material according to any one of 6 above.   8. The dye-forming coupler that forms the azomethine dye is contained in an amount of 24% by mass to 80% by mass with respect to the total lipophilic component in the layer containing the dye-forming coupler. The silver halide color photographic light-sensitive material according to any one of the above. A photosensitive silver halide emulsion layer containing a yellow dye-forming coupler, a photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, a photosensitive silver halide emulsion layer containing a cyan dye-forming coupler, and a non-photosensitive hydrophilic colloid layer on a support An image forming method in which a silver halide color photographic light-sensitive material having at least one layer each is exposed and developed, and at least one of the dye-forming couplers reacts with an oxidant of an aromatic amine compound to produce acetic acid. Dye-forming coupler which forms an azomethine dye having a solubility in ethyl of 1 × 10 ⁻⁸ mol / L or more and 5 × 10 ⁻³ mol / L or less, and wherein the silver halide color photographic light-sensitive material forms the azomethine dye Is contained in an amount of 18% by mass to 100% by mass with respect to the total lipophilic component of the layer containing the dye-forming coupler, and Image forming method characterized by comprising at least one at least one layer a compound represented by the following general formula (I) in the light-sensitive hydrophilic colloid layer.

In general formula (I), R ^{21 to} R ²⁹ may be the same or different and each represents a hydrogen atom or a substituent. However, at least one of R ^{21 to} R ²⁹ is a substituent. R ^{21 to} R ²⁹ may be a divalent group, and may be combined with a dimer or other monomer or a polymer chain to form a monopolymer or a copolymer. The silver halide emulsion layer containing at least one dye-forming coupler for forming the azomethine dye has a total dye-forming coupler coating amount of 0.18 mmol / m ^{2 to} 0.28 mmol / m ² and the dye The image forming method according to claim 9, wherein the maximum optical reflection density at the maximum absorption wavelength of the dye after formation is 2.0 or more.   11. The image forming method according to claim 9, wherein the color development time is 30 seconds or less in the development processing. The image forming method according to claim 9, wherein the exposure is 1 × 10 ⁻⁴ seconds or less.