JP2003307822A - Silver halide color photosensitive material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive material having excellent color reproducibility and stability in a dot area modulated color proof and capable of forming high throughput image and to provide an image forming method. <P>SOLUTION: The silver halide color photosensitive material has on a support at least one silver halide emulsion layer containing a cyan dye forming coupler, at least one silver halide emulsion layer containing a magenta dye forming coupler and at least one silver halide emulsion layer containing a yellow dye forming coupler and is exposed on the basis of digital image data for dot gradation, wherein the yellow dye forming coupler is represented by formula (I), where Q is a group of nonmetallic atoms forming a 5- to 7-membered ring together with -N=C-N(R1)-; R1 is a substituent; R2 is a substituent; m is an integer of 0 to 5; when m is ≥2, a plurality of symbols R2 may be the same or different and may combine to each other to form a ring; and X is H or a group which can be released by a coupling reaction with the oxidized body of a developing agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide color light-sensitive material and an image forming method. More specifically, the present invention relates to a silver halide color light-sensitive material that forms a color image based on area-modulated image data, and further, a color image for correction (color proof in a color plate making and printing process, which is similar to printing. The present invention relates to a silver halide color light-sensitive material suitable for producing a). The present invention relates to an image forming method using the above silver halide color light-sensitive material, particularly to a method for forming a high-definition color image, and a direct digital color proof (Direct Digi) using the silver halide color light-sensitive material.
tal Color Proof: DDCP).

[0002]

2. Description of the Related Art In recent years, with the progress of digitization of images, CTP (Computer To Plate)
It has become possible to print by a process that does not use a lith film. Along with this, the importance of a color proof for confirming a printed document has increased significantly. The proofs for digitalization are 1) low cost typified by inkjet method, but low quality proof that can hardly reproduce halftone dots, and 2) high cost and productivity typified by laser thermal method. Although it is low, it is possible to use this paper, high-quality proof that can reproduce halftone dots and color reproduction that is almost like printed matter, and 3) High quality silver halide color light-sensitive material that emphasizes productivity and cost performance. The proof used is used.

On the other hand, the direct digital color proof generally provides color reproducibility as close as possible to printing ink, has high resolution, has high productivity, can obtain an output sample in a short time, and is stable. There is a demand for high quality and low cost, and even for proofs using a silver halide color light-sensitive material, there is a demand for a higher level than ever before.

The system using a silver halide color light-sensitive material has conventionally used a light-sensitive material (reversal light-sensitive material) using a positive type silver halide emulsion. However, in recent years, with the digitization of plate data, it has become possible to perform reversal by calculation, and since the reversal function is not necessarily required as a photosensitive material, it has been used for color paper (photographic paper) and the like. Construction of a proof system using a light-sensitive material using negative-working negative silver halide has been studied. The above-mentioned requirements (1) are common to both positive and negative types, but in any case, color reproducibility is an extremely essential requirement for color proof, and further improvement is required. There is something.

As a result of diligent studies, the present inventors have found that when a negative type silver halide emulsion is used, a combination of coloring material technology for color paper and emulsion technology for high-intensity exposure (extremely short-time exposure) Faithfully halftone dots, thin lines,
It was found that a digital proof system can be constructed which has many advantages such as color reproduction, shortening of development processing time, cleaning of processing solution, and cost reduction.
However, one of the problems of the system using the negative type photosensitive material when forming an image mainly near the maximum density is that the deterioration of color reproduction due to the stain due to the excessive oxidized form of the developing agent becomes a problem. understood. This effect is remarkable in the high contrast light-sensitive material (because of the large amount of silver) which mainly uses the area gradation and the maximum density. Conventionally, this problem has been dealt with by a so-called processing color mixture improving technique in which a compound that reacts with an oxidized product of a developing agent is introduced into an intermediate layer or an emulsion layer. However, the use of these compounds is accompanied by side effects such as lowering the maximum color density, softening gradation, and deteriorating light resistance.

[0006]

The object of the present invention is to overcome the above problems. More specifically, the object of the present invention is, firstly, in an area-modulated color proof,
An object of the present invention is to provide a light-sensitive material and an image forming method capable of forming an image with excellent color reproducibility and stability and high productivity. Secondly, a silver halide color light-sensitive material which is excellent in stability, productivity, color reproducibility, and cost in a color image forming method mainly using the highest color density and having a large amount of coated silver. Is to provide. further,
Thirdly, in an image forming method using a negative tone type silver halide photographic light-sensitive material having a high contrast for forming a high-definition image, gradation characteristics by a semiconductor laser or LED scanning exposure method are good (in a high contrast), and An object of the present invention is to provide an image forming method that enhances color reproducibility.

[0007]

As a result of intensive studies, the inventors of the present invention have found that the above-mentioned objects of the present invention can be achieved by the following constitutions, and have completed the present invention. . (1) At least a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are each formed on a support. A silver halide color light-sensitive material having one layer and exposed based on digital image data for area gradation, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I). A silver halide color light-sensitive material characterized by:

[0008]

[Chemical 5]

In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (2) At least a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are each formed on a support. A silver halide color having one layer and forming an image using substantially the maximum density of each photosensitive layer (in the present invention, the maximum density part on the characteristic curve) without using the density of the gradation part. A silver halide color light-sensitive material, which is a light-sensitive material, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I).

[0010]

[Chemical 6]

In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (3) At least a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are each formed on a support. A silver halide color light-sensitive material having one layer and capable of drawing a fine line having a line width of 30 μm or less, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I). And a silver halide color light-sensitive material.

[0012]

[Chemical 7]

In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (4) In the general formula (I), Q is -C (-R11).
_{= C (-R12) - SO 2} - or -C (-R11)
= C (-R12) -CO-group (R11, R1
2 is a group which is bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently is a hydrogen atom or a substituent), and any one of (1) to (3) 2. A silver halide color light-sensitive material as described in the above item. (5) In the general formula (I), Q is -C (-R11).
_{= C (-R12) - SO 2} - group represented by (R11, R
12 is a group which is bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently is a hydrogen atom or a substituent), (1) to (3) 2. A silver halide color light-sensitive material as described in the above item. (6) Any one of (1) to (5), wherein the yellow dye-forming coupler represented by the general formula (I) is a yellow dye-forming coupler represented by the following general formula (II). A silver halide color light-sensitive material as described in the above item.

[0014]

[Chemical 8]

In the formula, 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 and may be bonded to each other to form a ring. R3 represents a substituent. n represents an integer of 0 or more and 4 or less. When n is 2 or more, a plurality of R3s may be the same or different and may combine with each other to form a ring. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (7) The silver halide color light-sensitive material according to item (6), wherein in the dye-forming coupler represented by the general formula (II), R1 is a substituted or unsubstituted alkyl group. (8) The silver halide color light-sensitive material is a negative type silver halide color light-sensitive material (1)
~ The silver halide color light-sensitive material according to any one of (7) to (7). (9) At least a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are each formed on a support. An image forming method in which a silver halide color light-sensitive material having one layer is exposed and then subjected to color development, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I), and An image forming method, which comprises exposing based on gradation digital image data.

[0016]

[Chemical 9]

In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (10) At least a silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are each provided on a support. An image forming method comprising subjecting a silver halide color light-sensitive material having one layer to color development processing after exposure, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I), and An image forming method characterized in that an image is formed using substantially only the maximum density of each photosensitive layer without using the density of the toned portion.

[0018]

[Chemical 10]

In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (11) The image forming method described in any one of (9) to (10), wherein the silver halide color light-sensitive material is a negative type silver halide color light-sensitive material. In the present invention, "for area gradation" means "for area gradation" in which density is expressed by the area gradation method.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
First, the compound represented by formula (I) of the present invention (also referred to as a dye-forming coupler in the present application) will be described in detail.

[0021]

[Chemical 11]

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, (Including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio , 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 heterocyclic azo group, imide Group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.

The above-mentioned substituent may be further substituted with a substituent, and examples of the substituent include the above-mentioned 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, and 11 or more and 4
0 or less is more preferable, and 16 or more and 30 or less is most preferable. When R1 is a substituted alkyl group, examples of the substituent include the examples of the substituent of R1 described above. The carbon number of the alkyl group of R1 is preferably 1 to 40, more preferably 3 to 36, and further preferably 8 to 3
It is 0. This preferred order is not particularly dependent on Q, but especially when Q described below is -C (-R11) = C (-R
12) -It is preferable in the case of a group represented by -CO-.

R1 is preferably 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-, 3- or 4-position, and more preferably 16 or more carbon atoms. An unsubstituted alkyl group or an alkyl group substituted with an alkoxy group or an aryloxy group at the 3-position, 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 the general formula (I), Q is -N = C-N
(R1) -represents a non-metal atom group forming a 5- to 7-membered ring with (R1)-. The 5- to 7-membered ring formed is preferably a substituted or unsubstituted, monocyclic or condensed ring heterocycle, and more preferably the ring-constituting atom is selected from a carbon atom, a nitrogen atom and a sulfur atom. More preferably Q is -C (-
R11) = C (-R12) -SO 2 -, or -C
It represents a group represented by (-R11) = C (-R12) -CO- (in the present invention, the notation of these groups does not limit the bonding direction of the groups represented by these groups). Of these, Q is preferably -C (-R11) = C (-R1).
It represents a group represented by - ₂₎ -SO 2. R11 and R12 are bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently represent a hydrogen atom or a substituent. The 5- to 7-membered ring formed is a saturated or unsaturated ring, and the ring may be an alicyclic ring, an aromatic ring, or a hetero ring, for example, a benzene ring, a furan ring, a thiophene ring, a cyclopentane ring. , And a cyclohexane ring. Examples of the substituent include the examples given above as the substituent of R1.

Each of these substituents and the ring formed by combining a plurality of substituents with each other may be further substituted with a substituent (the groups exemplified as the above-mentioned substituents of R1).

In the general formula (I), R2 represents a substituent other than a hydrogen atom. Examples of this substituent include R1 described above.
The examples of the substituents of are listed. 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 acetamide), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (Eg methoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl), carbamoyl group (eg N-methylcarbamoyl, N, N-
Diethylcarbamoyl), sulfamoyl groups (eg N
-Methylsulfamoyl, N, N-diethylsulfamoyl), alkylsulfonyl group (eg methanesulfonyl), arylsulfonyl group (eg benzenesulfonyl), alkylthio group (eg methylthio, dodecylthio), arylthio group (eg phenylthio, naphthylthio) ), A cyano group, a carboxyl group, and a sulfo group.
When R2 is in the ortho position with respect to the -CONH- group, it is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylthio group or an arylthio group. In the present invention, at least one R2 is-
It is preferably in the ortho position with respect to the CONH-group.

In the general formula (I), 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 and may be bonded to each other to form a ring. m is preferably 0 to 3, more preferably 0 to 2, even more preferably 1 to 2, and most preferably 2.

In the general formula (I), X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. When X is a group capable of leaving by a coupling reaction with an oxidized product of a developing agent, examples thereof include a group capable of leaving at a nitrogen atom, a group capable of leaving at an oxygen atom, a group capable of leaving at a sulfur atom, and a halogen atom (for example, a chlorine atom). , Bromine atom) and the like. The group capable of leaving at the nitrogen atom includes a heterocyclic group (preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic (in the present application, means one having 4n + 2 cyclic conjugated electrons) or non- Aromatic, monocyclic or condensed ring heterocyclic group, more preferably, the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom, and any hetero atom of nitrogen atom, oxygen atom and sulfur atom A 5- or 6-membered heterocyclic group having at least one of, for example, succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole. , Benzotriazole, imidazoline-2,4-dione, oxazo Jin-2,4-dione, thiazolidin-2-one, Benz imidazoline -
2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione,
2,6-Dioxypurine parabanic 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 group (eg acetamide, trifluoroacetamide), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), arylazo group (eg phenylazo, naphthylazo), carbamoylamino group ( For example, N-methylcarbamoylamino) and the like can be mentioned.

Of the groups capable of splitting off at a nitrogen atom, a heterocyclic group is preferred, and a more preferred one is an aromatic heterocyclic group having 1, 2, 3 or 4 nitrogen atoms as ring-constituting atoms, or It is a heterocyclic group represented by the general formula (L).

[0032]

[Chemical 12]

In the formula, L is 5 to 6 together with -NC (= O)-.
Represents a residue forming a nitrogen-containing heterocycle of a member ring. Examples of these are given in the above description of the heterocyclic group, and these are more preferable. Among them, L is preferably a residue forming a 5-membered nitrogen-containing heterocycle.

The group capable of leaving at an oxygen atom includes an aryloxy group (eg phenoxy, 1-naphthoxy), a heterocyclic oxy group (eg pyridyloxy, pyrazolyloxy), an acyloxy group (eg acetoxy, benzoyloxy), an alkoxy group (eg Methoxy, dodecyloxy), carbamoyloxy group (eg N, N-diethylcarbamoyloxy, morpholinocarbamoyloxy), aryloxycarbonyloxy group (eg phenoxycarbonyloxy), alkoxycarbonyloxy group (eg methoxycarbonyloxy, ethoxycarbonyloxy) , Alkylsulfonyloxy groups (eg methanesulfonyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy, toluenesulfonyloxy), etc. It is below. Of the groups capable of leaving at an oxygen atom, preferred are an aryloxy group, an acyloxy group and a heterocyclic oxy group.

Examples of the group capable of splitting off with a sulfur atom include an arylthio group (eg phenylthio, naphthylthio), a heterocyclic thio group (eg tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxazolylthio, benzimidazolyl). Thio), alkylthio groups (eg methylthio, octylthio, hexadecylthio), alkylsulfinyl groups (eg methanesulfinyl), arylsulfinyl groups (eg benzenesulfinyl), arylsulfonyl groups (eg benzenesulfonyl), alkylsulfonyl groups (eg methanesulfonyl), etc. Is mentioned. Of the groups capable of splitting off at a sulfur atom, an arylthio group and a heterocyclic thio group are preferable, and a heterocyclic thio group is more preferable.

X may be substituted with a substituent,
Examples of the substituent for substituting X include those mentioned above as examples of the substituent for R 1. X is preferably a group capable of leaving by a coupling reaction with an oxidized product of a developing agent, and among such leaving groups, a group capable of leaving at a nitrogen atom, a group capable of leaving at an oxygen atom, and a group capable of leaving at a sulfur atom. And more preferably a group capable of leaving at a nitrogen atom, and even more preferably the preferred groups described in the group capable of leaving at a nitrogen atom. Explaining further the preferable group of X, a group capable of leaving at a nitrogen atom is preferable, but an aromatic heterocyclic group having at least two (preferably two) nitrogen atoms (preferably a 5-membered aromatic heterocyclic group , A pyrazole group which may have a substituent) or a group represented by the general formula (L) is particularly preferable.

X may be a photographically useful group. Examples of the photographically useful group include a development inhibitor, a desilvering accelerator, a redox compound, a dye, a coupler and the like, or a precursor thereof. In the present invention, it is preferable that the photographically useful group as described above is not used.

In order to immobilize the coupler in the light-sensitive material, at least one of Q, R1, X and R2 preferably has a total carbon number including the substituents of 8 or more and 50 or less, and more preferably. The total carbon number is 10 or more and 40 or less.

Among the compounds represented by the general formula (I) of the present invention, preferred compounds can be represented by the following general formula (II). The compound represented by formula (II) of the present invention (also referred to as a dye-forming coupler in the present application) is described in detail below.

[0040]

[Chemical 13]

In the general formula (II), R1, R2, m,
X represents the same as described in formula (I), and the preferable range is also the same.

In the general formula (II), R3 represents a substituent. Examples of the substituent include those mentioned above as examples of the substituent of R1. 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 ( For example, phenoxy), acyloxy group (for example, acetyloxy), amino group (for example, dimethylamino, morpholino), acylamino group (for example, acetamide), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (for example, methoxycarbonyl). ), An aryloxycarbonyl group (eg phenoxycarbonyl), a carbamoyl group (eg N-methylcarbamoyl, N, N-diethylcarbamoyl), a sulfamoyl group (eg N-methyls). Famoiru, 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, a plurality of R3s may be the same or different and may combine with each other to form a ring.

Among the couplers represented by formula (I) or formula (II) in the present invention, preferred specific examples are shown below, but the present invention is not limited thereto. In addition, the hydrogen atom at the coupling position (hydrogen atom on the carbon atom to be substituted by X) is C = bonded to the coupling position.
The present invention also includes tautomers that have moved to the nitrogen atom of the N portion (a ring-constituting nitrogen atom to which R1 is not bonded).

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

In the following description, when the exemplified compounds shown above (also referred to as dye-forming couplers) are cited, the number (x) in parentheses attached to each exemplified compound is used to indicate "coupler". (X) ”will be displayed.

Specific synthetic examples of the compounds represented by the above general formula (I) or general formula (II) are shown below.

Synthesis Example 1: Synthesis of coupler (1) The coupler (1) was synthesized by the route shown below.

[0057]

[Chemical formula 24]

To a solution of 38.8 g of a 40% aqueous methylamine solution and 200 ml of acetonitrile, 44.3 g of ortho-nitrobenzenesulfonyl chloride was added little by little while cooling with ice. The system temperature was raised to room temperature and further stirred for 1 hour. Ethyl acetate and water were added for liquid separation,
The organic layer was washed with diluted hydrochloric acid and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 28.6 g of compound (A-1).

Reduced iron 44.8 g, ammonium chloride 4.
5 g of the product was dispersed in 270 ml of isopropanol and 45 ml of water and heated under reflux for 1 hour. Compound (A-1) 2
5.9 g was added in small portions with stirring. After heating under reflux for a further 1 hour, suction filtration was performed through Celite. Ethyl acetate and water were added to the filtrate for liquid separation, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure to give compound (A-2) as an oily product 2
1.5 g was obtained.

A solution of 18.9 g of compound (A-2), 39.1 g of hydrochloride of imino ether (A-0) and 200 ml of ethyl alcohol was stirred under heating under reflux for 1 day. Furthermore, 19.2 g of hydrochloride of imino ether was added and further heated under reflux.
It was stirred for 1 day. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane to obtain 21.0 g of compound (A-3).

5.6 g of compound (A-3), 2-methoxy-5-tetradecyloxycarbonylaniline 7.2
A solution of 20 ml of g and m-dichlorobenzene was stirred for 6 hours while heating under reflux. After cooling, hexane was added to crystallize and 8.
8 g of compound (A-4) was obtained.

To a solution of 5.4 g of the compound (A-4) in 110 ml of methylene chloride, 10 ml of a methylene chloride solution of 0.45 ml of bromine was added dropwise under ice cooling. After stirring at room temperature for 30 minutes, methylene chloride and water were added for liquid separation, and the organic layer was washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude compound (A-5).

5,5-Dimethyloxazolidine-2,4
-Dione 3.5 g, triethylamine 3.8 ml N,
A solution prepared by dissolving 110 ml of N-dimethylacetamide and dissolving all of the crude compound (A-5) synthesized above in 25 ml of acetonitrile at room temperature was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with 0.1N aqueous potassium hydroxide solution, diluted hydrochloric acid solution and saturated saline solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of acetone and hexane as an eluent, ethyl acetate,
Crystallized from a mixed solvent of hexane and 4.7 g of coupler (1)
Got

Synthesis Example 2: Synthesis of coupler (3) The coupler (3) was synthesized by the route shown below.

[0065]

[Chemical 25]

3- (2,4-di-t-amylphenoxy) propylamine 438 g, triethylamine 210
To a solution of 1 ml of acetonitrile and 1 liter of acetonitrile, 333 g of ortho-nitrobenzenesulfonyl chloride was added little by little while cooling with ice. The system temperature was raised to room temperature and further stirred for 1 hour. Ethyl acetate and water were added for liquid separation,
The organic layer was washed with diluted hydrochloric acid and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization was performed from a mixed solvent of ethyl acetate and hexane to obtain 588 g of compound (B-1).

Reduced iron 84.0 g, ammonium chloride 8.
4 g was dispersed in 540 ml of isopropanol and 90 ml of water and heated under reflux for 1 hour. Compound (B-1) 11
9 g was added in small portions with stirring. After heating under reflux for a further 2 hours, suction filtration was performed through Celite. Ethyl acetate and water were added to the filtrate for liquid separation, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to obtain 111 g of an oily compound (B-2).

111 g of compound (B-2), 68.4 g of hydrochloride of imino ether (A-0), ethyl alcohol 1
50 ml of the solution was stirred with heating under reflux for 1 hour. Furthermore, 4.9 g of hydrochloride of imino ether was added, and the mixture was further heated under reflux for 3
Stir for 0 minutes. After cooling, suction filtration was carried out, 100 ml of p-xylene was added to the filtrate, and the mixture was heated under reflux for 4 hours while distilling off ethanol. The reaction solution was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent, and crystallized from methanol to give 93.1 g.
The compound (B-3) of was obtained.

A solution of 40.7 g of compound (B-3), 18.5 g of 2-methoxyaniline and 10 ml of p-xylene was stirred with heating under reflux for 6 hours. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent,
37.7 g of an oily compound (B-4) was obtained.

To a solution of 24.8 g of the compound (B-4) in 400 ml of methylene chloride, 35 ml of a methylene chloride solution of 2.1 ml of bromine was added dropwise under ice cooling. After stirring for 30 minutes under ice cooling, methylene chloride and water were added for liquid separation, and the organic layer was washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude compound (B-5).

5,5-Dimethyloxazolidine-2,4
Dione (15.5 g) and triethylamine (16.8 ml) were dissolved in N, N-dimethylacetamide (200 ml), and the crude product of the compound (B-5) synthesized above was dissolved in acetonitrile (40 ml) at room temperature. The mixture was added dropwise over minutes, the temperature was raised to 40 ° C., and the mixture was stirred for 30 minutes. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with 0.1N aqueous potassium hydroxide solution, diluted hydrochloric acid solution and saturated saline solution. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of acetone and hexane as an eluent, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 23.4 g of coupler (3).

The silver halide color light-sensitive material of the present invention will be described in detail below. The silver halide color light-sensitive material of the present invention is preferably applied to the production of digital color proofs. The proof light-sensitive material is generally a silver halide color light-sensitive material having a silver halide light-sensitive layer forming at least a yellow dye, a magenta dye, and a cyan dye on a support, and has a hue similar to that of a printing ink. And is exposed using three or more light source units having different wavelengths based on the halftone dot image information to form an area-modulated image. A fourth photosensitive layer may be provided for the purpose of achieving both black (chromaticity and Dmax) and solid solid (chromaticity and Dmax) (improving color reproducibility) and determining black plates. In this case, the exposure light source uses three or four light sources having different wavelengths. Although the exposure light source will be described in detail later, it often has a plurality (preferably 8 or more) of light source units of each color, and it is possible to use an LED, an LD, or another device. As the exposure light source, it is possible to use light sources of all wavelengths in the visible region and infrared region such as blue, green and red, and the combination thereof is also free.

The silver halide emulsion preferably used in the present invention will be described below. In the present invention, the silver halide grains include silver chloride, silver chlorobromide, silver bromide, silver iodobromide,
Although silver chloroiodobromide or the like can be used, it is preferable to use silver chloride, silver chlorobromide, or silver chloroiodobromide grains having 90 mol% or more of silver chloride. When using silver chloride,
The silver chloride content is preferably 95 mol% or more, 95 to 9
9.9 mol% is more preferable, and 98-99.9 mol% is still more preferable. In particular, in the present invention, in order to shorten the development processing time, silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The phrase "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.

On the other hand, on the surface of silver halide grains as described in JP-A-3-84545, for the purpose of enhancing the sensitivity of high illuminance, enhancing the sensitivity of spectral sensitization, or enhancing the stability of a light-sensitive material over time. In some cases, high silver chloride grains containing 0.01 to 3 mol% of silver iodide are preferably used. The halogen composition of the silver halide grains may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, and the core (core) inside the silver halide grains, Particles having a so-called layered structure in which the halogen composition is different from that of a shell (a single layer or a plurality of layers) surrounding the, or a structure having a portion having a different halogen composition in the inside or on the surface of the particle (on the particle surface) In this case, particles having a structure in which portions having different compositions are bonded to the edges, corners, or surfaces of the particles can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance.
When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change.

In the silver halide light-sensitive material of the present invention, the inside of the silver halide grain and / or the grain surface are
It is preferable to use a high silver chloride emulsion having a structure having a silver bromide localized phase in a layered or non-layered manner. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. The silver bromide content of the silver bromide localized layer is determined by X-ray diffractometry (for example, described in "Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis" Maruzen). Can be analyzed. The localized phase may be present inside the grain, on the edge of the grain surface, on the corner, or on the surface, but one preferable example thereof is that epitaxially grown on the corner portion of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 05 μm to 2 μm is preferable.
The coefficient of variation of those particle size distributions (standard deviation of particle size distribution divided by average particle size) is 20
% Or less, preferably 15% or less, more preferably 10%
The following monodisperse particles are particularly preferable. At this time, in order to obtain a wide latitude, it is also preferable to use the above monodisperse emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of the silver halide grains contained in the silver halide emulsion used in the present invention may be one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, a spherical shape or a plate shape. Those having an irregular crystal form, or those having a composite form thereof are used. Also, a mixture of materials having various crystal forms may be used. The silver halide emulsion used in the present invention contains 50% of the grains having the above-mentioned regular crystal form.
The above content is preferably 70% or more, more preferably 90% or more. In addition to these, it is preferable to use an emulsion having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more, and tabular grains having a projected area of more than 50% of all grains. it can.

The silver chloro (bromide) emulsion used in the present invention is P.Gl.
Chimie et Phisique Photographique (Paul by afkides
Montel, 1967), by GF Duffin Photographi
c Emulsion Chemistry (Focal Press, 1966
,) By VL Zelikman et al Making and Coating Phot
It can be prepared using a method described in, for example, ographic Emulsion (Focal Press, 1964).
That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. It is also possible to use a method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method). As one form of the simultaneous mixing method, pA in the liquid phase produced by silver halide
Method to keep g constant, that is, so-called controlled
The double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or a complex ion thereof. Group VIII, IIb of the Periodic Table
More preferred are metal ions belonging to the group, metal complexes, lead ions, and thallium ions. Ions selected from iridium, rhodium, iron, etc. or their complex ions are mainly used for the localized phase, and osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. are mainly used for the substrate. The metal ions selected from the above or complex ions thereof are used in combination.
Further, the type and concentration of the metal ion can be changed between the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

The metal ion may be contained in the emulsion grains in the form of a compound providing the metal ion, or may be contained in the emulsion phase in the form of a metal ion. The compound that provides the metal ion is a silver halide solution containing a metal ion in advance in a gelatin aqueous solution, a halide aqueous solution, a silver salt aqueous solution or another aqueous solution, which serves as a dispersion medium at the time of silver halide grain formation. It can be contained in the localized phase and / or other grain portion (substrate) of the silver halide grain by means such as adding in the form of fine grain and dissolving the fine grain. In addition, the incorporation of the metal ion in the emulsion grains can be carried out either before grain formation, during grain formation, or immediately after grain formation,
It can be appropriately determined depending on at which position of the emulsion grains metal ions are incorporated. For the silver halide light-sensitive material of the present invention, it is necessary to use a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention contains various compounds or their compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage and photographic processing, and stabilizing photographic performance. A precursor can be added. Specific examples of these compounds are described in JP-A-62-2152.
Those described on pages 39 to 72 of the specification of Japanese Patent Publication No. 72 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

The silver halide emulsion used in the present invention is
It is preferable to use inorganic sulfur for chemical sensitization, but the present invention is not limited thereto. There are several allotropes of inorganic sulfur, but any allotrope may be used as the inorganic sulfur used in the present invention. Of allotropes, it is preferable to use α-sulfur that is stable around room temperature. The inorganic sulfur may be added before or after the gold compound is added, or at any timing from the grain formation to the end of the chemical sensitization, but it is preferably before the gold compound is added. The addition amount is preferably 10 ^-10 to 10 ^-4 mol, and 10 ^-9 to 10 ^-10 mol per mol of silver halide.
^-7 mol is more preferred. The silver halide emulsion used in the present invention is usually chemically and spectrally sensitized, but the present invention is not limited thereto. It is necessary to use a gold compound for chemical sensitization of the silver halide emulsion used in the present invention, and the gold compound used for this is
It is preferable to use a compound such as chloroauric acid or a salt thereof, gold thiocyanate, gold thiosulfate, or gold sulfide colloid. Chemical sensitization using a chalcogen sensitizer for chemical sensitization with a gold compound (specifically, sulfur sensitization represented by addition of an unstable sulfur compound, or selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound. Sensitization), noble metal sensitization other than gold compounds, reduction sensitization, and the like can be used in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the silver halide light-sensitive material of the present invention. In the silver halide light-sensitive material of the present invention, the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions is, for example, Heter by FM Harmer.
ocyclic compounds-Cyanine dyes and related compoun
ds (John Wiley & Sons [New York, London] 196
4 years). Examples of specific compounds and the spectral sensitization method are described in JP-A-62-1
Those described in the upper right column on page 22 to page 38 of 215272 gazette are preferably used. As a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dyes described in JP-A-3-123340 are stable, have strong adsorption, and have an exposure temperature. It is particularly preferable from the viewpoint of dependency and the like.

In the silver halide light-sensitive material of the present invention,
To efficiently spectrally sensitize the infrared region, JP-A-3-150
No. 49, page 12, upper left column to page 21, lower left column, JP-A-3-2
No. 0730, page 4, lower left column to page 15, lower left column, EP-0,
No. 420, 011, page 4, line 21 to page 6, line 54, EP-0,
No. 420, 012, page 4, line 12 to page 10, line 33, and EP
The sensitizing dyes described in -0,443,466 and US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve and 2,2,2. You may melt | dissolve in 1 type of solvent or 2 or more types of mixed solvent selected from 3,3-tetrafluoro propanol etc., and may add it to an emulsion. JP-B-44-23389, JP-B-44-275
55, JP-B No. 57-22089, etc., to form an aqueous solution by coexisting an acid or a base, or US Pat. No. 3,822,135 and US Pat. No. 4,006,025.
An aqueous solution or a colloidal dispersion may be added to the emulsion in the presence of a surfactant as described in the specification and the like. Alternatively, the emulsion may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion. Furthermore, JP-A-53-1
As described in JP-A-02733 and JP-A-58-105141, the dispersion may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion.

Regarding the timing of addition to the emulsion,
It may be at any stage of emulsion preparation known to be useful as a timing of addition. That is, a coating solution is prepared before grain formation of a silver halide emulsion, during grain formation, immediately after grain formation, before entering a washing step, before chemical sensitization, during chemical sensitization, and immediately after chemical sensitization until the emulsion is cooled and solidified. You can choose from either time or. Most commonly, after the completion of chemical sensitization and before application, US Pat. No. 3,62.
As described in JP-A-8,969 and JP-A-4,225,666, spectral sensitization can be performed simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer. 58
It can also be carried out prior to the chemical sensitization as described in JP-A-113928. It is also possible to start the spectral sensitization by adding the silver halide grains before the completion of precipitation formation. Furthermore, as taught in U.S. Pat. No. 4,225,666, it is possible to add the spectral sensitizing dyes separately, i.e., a portion prior to the chemical sensitization and the balance chemically. It can be added after sensitization and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Among these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The preferable range of the amount of the spectral sensitizing dye added is, depending on the case, a wide range, preferably 0.5 × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol per mol of silver halide. It is more preferably from 0.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol.

In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, it is disclosed in JP-A No.
It is preferable to use the compounds described in JP-A-157749, page 13, lower right column to page 22, lower right column in combination. By using these compounds, the storability and processing stability of the light-sensitive material and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the publication in combination. These compounds are used in an amount of 0.5 × 10 ⁻⁵ mol to 5.0 mol per mol of silver halide.
× 10 ^-2 mol, preferably 5.0 × 10 ^-5 mol to 5.0
An amount of × 10 ^-3 mol is used, and is 0.1 to 10,000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous usage of 0 times.

The color light-sensitive material of the present invention has at least a yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer, and a cyan image forming silver halide emulsion layer, and is contained in each emulsion layer. Silver halides have different maximum spectral sensitivity wavelengths. In the present invention, an image is formed by exposing with a laser or a light emitting diode having a wavelength corresponding to the spectral wavelength region of each emulsion layer, and at least one of the reflection densities of the raw sample measured at the wavelength of the exposure. Is 0.8 or more, and more preferably 1.0 or more. The reflection density before the development processing is set to 0.
As a method of increasing the number to 8 or more, a method of adding a water-soluble dye having absorption in at least the spectral sensitivity region of the silver halide emulsion and / or a method of providing an antihalation layer in the lowermost layer or other layers are preferable. Further, a method in which a solid disperse dye is contained in a light-sensitive material to suppress the diffusion of the dye in the light-sensitive material can be mentioned. Examples of the water-soluble dye used in the present invention include dyes such as oxonol, cyanine, merocyanine, azo, anthraquinone, and allylidene, but they have high decomposability in a development processing bath and no increase in silver halide emulsion. From the viewpoint of feeling, particularly preferable dyes are oxonol dyes and merocyanine dyes. Oxonol dyes are described in US Pat. No. 4,187,
225, JP-A-48-42826, 49-512.
5, No. 49-99620, No. 50-91627,
51-77327, 55-120660, 5
8-24139, 58-143342, 59-
No. 38742, No. 59-111640, No. 59-11.
1641, 59-168438, 60-218.
No. 641, No. 62-31916, No. 62-66275.
No. 62-66276, No. 62-185755,
Nos. 62-273527 and 63-139949. In addition, merocyanine dyes are disclosed in
0-145124, 58-120245, 63.
-35437, 63-35438, 63-34.
539, 63-58437 and the like.
The amount of the water-soluble dye to be used is singly or in combination of two or more so that the reflection density of the raw sample before development processing measured by the wavelength of the laser or the light emitting diode for exposing the light-sensitive material is 0.8 or more. Select and add.

In the present invention, an antihalation layer may be provided on the bottom layer or other layers. The antihalation layer contains a compound that absorbs light. Examples of the compound that absorbs light include various organic compounds and inorganic compounds that have the action. As the inorganic compound, colloidal silver, colloidal manganese and the like are preferable, but colloidal silver is preferable. The above colloidal silver is, for example, reduced by keeping alkaline in gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol or dextrin, and then neutralizing and cooling to set gelatin. It is obtained by removing the reducing agent and unnecessary salts by the noodle washing method. When the colloidal silver particles are produced in the presence of an azaindene compound or a mercapto compound when reducing with an alkaline solution, a colloidal silver dispersion liquid having uniform particles can be obtained. The amount of colloidal silver applied is 0.5 for the reflection density of the raw sample.
Amounts of up to 1.5 are preferred.

In the color light-sensitive material of the present invention, at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group is contained in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers. The dye can be contained as a solid disperse dye in a solid dispersion. The support preferably used in the present invention, both sides of the paper substrate is coated with a resin containing a polyolefin resin as a main component, the unevenness of the surface of the support is continuously measured,
When the measured signal is obtained by frequency analysis, the integrated value (PY value) of the power spectrum in the frequency section of 1 to 12.5 mm on the surface of the support is preferably 2.9 μm or less. The PY value is more preferably 1.8 μm or less, still more preferably 1.15 μm or less. PY value is 2.9μ
If a support larger than m is used, the unevenness of the image becomes large and the dot reproduction deteriorates when the drum rotation speed is increased to improve the productivity. To measure this PY value, a film thickness continuous measuring machine (for example, manufactured by Anritsu Corporation) is used to continuously measure the thickness unevenness of the polyolefin-coated support, and the obtained measurement signal is analyzed by a frequency analyzer (for example, Hitachi It is obtained by frequency analysis using an electronic company: VC-2403).

The support can be arbitrarily selected from the supports generally used for photographic printing papers and films. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for paper making.
Generally, a natural pulp mainly composed of a softwood pulp, a hardwood pulp, a mixed pulp of a softwood pulp and a hardwood pulp, etc. can be widely used. Furthermore, in the support,
Additives such as sizing agents, fixing agents, strength enhancers, fillers, antistatic agents, dyes and the like generally used in papermaking may be blended, and surface sizing agents, surface tenacity agents, antistatic agents, etc. may be appropriately added. It may be applied on the surface. As the reflective support, one having a smooth surface having a mass of 50 to 300 g / m ² is usually used, and the resin for laminating both surfaces thereof is a homopolymer of ethylene, α-olefins such as polypropylene. , A copolymer of at least two kinds of the above-mentioned olefins, or a mixture of at least two kinds of these various polymers, and the like. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof. The molecular weight of the polyolefin resin to be laminated on the reflective support is not particularly limited, but normally one in the range of 20,000 to 200,000 is used.

The polyolefin resin coating layer on the side of the reflective support on which the photographic emulsion is coated preferably has a thickness of 25 to 50 μm, more preferably 25 to 35 μm. The polyolefin used to laminate the back side of the reflective support (the reflective side of the side on which the emulsion layer is provided) is usually a melt-laminated mixture of low and high density polyethylene. And, in general, this layer is often matted. In addition, cellulose triacetate film (TAC), polyethylene terephthalate (P
Various film supports such as ET) and polyethylene terephthalate (PEN) are also preferably used.

When forming a laminate on the front and back of the support,
In general, in order to improve the flatness of the developed photographic paper in a normal environment, a means such as slightly increasing the density of the resin layer on the front side than the back side or increasing the laminating amount on the back side than the front side is used. Generally, the front and back surfaces of the reflective support can be laminated on the support by a melt extrusion coating method. In addition, it is preferable to perform corona discharge treatment, flame treatment, or the like on the surface of the support or on both the front and back surfaces as necessary. Further, a subcoat layer for improving the adhesiveness with the photographic emulsion may be provided on the surface of the surface laminate layer, or a backcoat layer for improving the printability and antistatic property may be provided on the laminate layer on the back surface. preferable.

The polyolefin resin used for laminating the surface of the support (the surface on which the emulsion layer is provided) is dispersed and mixed with a white pigment in an amount of preferably 13 to 20% by mass, more preferably 15 to 20% by mass. An inorganic and / or organic white pigment can be used as the white pigment, and an inorganic white pigment is preferable. Examples thereof include alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, oxidization. Examples thereof include titanium, zinc oxide, talc, clay and the like. Of these, barium sulfate, calcium carbonate and titanium oxide are preferable, and barium sulfate and titanium oxide are more preferable. The titanium oxide may be rutile type or anatase type, and the surface thereof is hydrous alumina.
Those coated with a metal oxide such as hydrous ferrite can also be used. In addition, it is preferable to add an antioxidant, a colored pigment for improving whiteness, and a fluorescent whitening agent. Further, by coating a hydrophilic colloid layer containing a white pigment on the reflective support, the sharpness is improved, which is preferable. As the white pigment, the same white pigment as described above can be used, but titanium oxide is preferable. It is more preferable to add a hollow fine particle polymer or a high boiling point organic solvent to the hydrophilic colloid layer containing a white pigment, since the sharpness and / or curl resistance can be improved.

The surface shape of the reflective support may be smooth or have an appropriate surface roughness, but it is preferable to select a reflective support having a gloss close to that of a printed matter. For example, JIS B 0601-197
6 has an average surface roughness SRa of 0.30 to 3.0.
Preference is given to using a white support which is μm. In the light-sensitive material of the present invention, the surface roughness of the image forming surface is 0.30-3.
It is preferable that the particle size be 0 μm, and therefore it can be adjusted by incorporating a fine particle powder. This fine particle powder is often referred to in the art as a matting agent, and therefore, hereinafter, will be referred to as a matting agent unless otherwise specified. As the layer to which the matting agent is added, there are a silver halide emulsion layer, a protective layer, an intermediate layer, an undercoat layer and the like, which may be added to a plurality of layers. It is preferably the uppermost layer of the light-sensitive material. The surface gloss of the light-sensitive material on the image forming layer side preferably has a gloss close to that of a printed matter. For example, the glossiness GS (60 °) of the surface of the image-forming layer after the treatment is measured by the method specified in JIS Z 8741. Is preferably 5 to 60. In a preferred embodiment of the present invention, it is preferable to form a protective layer on the outermost surface of the light-sensitive material and add a matting agent to the protective layer.

Examples of the matting agent which can be used in the present invention include crystalline or amorphous silica, titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, strontium barium sulfate, magnesium aluminate silicate, silver halide and silicon dioxide. , Acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, itaconic acid-styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-
Examples thereof include a styrene copolymer, an acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, an acrylic acid-methacrylic acid-ethyl methacrylate copolymer, polystyrene, starch, and cellulose acetate propionate.

Others, US Pat. No. 1,221,980
No. 2,992,101, and the like, and these can be used alone or in combination of two or more kinds. Colloidal silica may be used together with the matting agent. The particle size of these matting agents is preferably 1 to 10 μm in average particle size, more preferably 3 to 10 μm.
m. The average particle size (referred to as rm) referred to here is the diameter of spherical particles, and in the case of cubic or non-spherical particles, the projected image is converted into a circular image of the same area. Is the average value of the diameter of the
Then, when the number is ni, it is defined by the following equation. As a specific measuring method, the method described in JP-A-59-29243 can be applied.

Rm = Σniri / Σni In the present invention, the matting agent is dispersed and contained in the layer on the side opposite to the photosensitive layer. As a method for this, a nonionic, cationic or anionic interface is used, if necessary. In a hydrophilic binder containing an activator, if necessary, other additives are added, and the mixture is dispersed by an emulsion dispersion method utilizing shear stress by a high-speed rotary mixer, a homogenizer, ultrasonic dispersion, a ball mill, etc. Can be applied to form. The coating amount of the matting agent is 50 to ⁵ per 1 m ^{2 of the} layer to be included.
00 mg is preferred, more preferably 70-300 mg
Is. Further, the content of the matting agent is preferably 3 to 50% by mass (wt%) with respect to the hydrophilic binder, and more preferably 5 to 20% by mass (wt%). Further, in the present invention, a synthetic resin film support such as polypropylene whose surface is further coated with polyolefin can be used. The thickness of the reflective support is not particularly limited, but is 80-
One having a thickness of 160 μm is preferably used. Especially 90 ~
The thickness of 130 μm is more preferable.

The reflection support of the light-sensitive material used in the present invention has a mass per m ² of 130 g or less, more preferably 70 to 120 g per m ² . The support used for the light-sensitive material has a Taber stiffness (Tabe stiffness).
It is preferable that r Stiffness) is 0.8 to 4.0. The Taber stiffness is a stiffness measuring instrument V-5 model 150B (Taber V-5 St) as a measuring instrument.
ifness tester: TABER INST
RUMENT-A TELEDYNE COMPANY
Manufactured). The rigidity value of the support is generally different in the longitudinal direction and the lateral direction, but at least one of the supports may be in the above range.

The yellow dye-forming coupler, which is contained in a layer other than the yellow image-forming layer of the present invention and is used for adjusting the hue, is a yellow dye-forming coupler reacted with the developing agent of the present invention in a medium such as a high boiling solvent. Any dye-forming coupler which can be used to provide the image with the spectral absorption of the present invention may be used. Preferred yellow dye-forming couplers are represented by the general formula (Y-
It is a dye-forming coupler represented by I).

[0101]

[Chemical formula 26]

In the general formula (Y-I), Y represents an alkoxy group, a branched alkyl group, a substituted phenyl group and a nitrogen-containing heterocyclic group, and Z represents a substituted aryl group. X is a hydrogen atom,
Alternatively, it represents a group capable of leaving by the reaction with the oxidized form of the developer. The yellow dye-forming coupler represented by formula (Y-I), which is preferably used in the invention, will be described in detail.

Y represents an alkoxy group, a branched alkyl group, a substituted phenyl group or a nitrogen-containing heterocyclic group. When Y represents an alkoxy group, it preferably has 1 to 30 carbon atoms, and 1 to 1 carbon atoms.
12 is more preferable. For example, methoxy, ethoxy, isopropoxy, t-butoxy, cyclohexyloxy and the like can be mentioned. When Y represents a branched alkyl group, the number of carbon atoms is
3-30 are preferable and C3-C12 is more preferable.
Examples thereof include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropyl group and a t-butyl group. When Y represents a substituted phenyl group, the substituent is
The substituents described for R1 in formula (I) can be mentioned.

Among the above, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group. The sulfamoyl group also includes those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group,
Examples thereof include ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group and sulfamoyl group.

Of the above-mentioned substituents, preferred are an alkyl group, an alkoxy group, an aryl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an acylamino group and a sulfonamide group, and a more preferred substituent is an alkyl group. , Alkoxy groups, with alkoxy groups being the most preferred substituents. Among the alkoxy,
A methoxy group is more preferred. The number of substituents on the phenyl group is preferably 0 to 4, more preferably 1 to 3,
More preferably, it is 1, and the substitution position is preferably the para position with respect to the carbonyl group.

When Y represents a nitrogen-containing heterocyclic group, the ring portion of Y may be a saturated ring or an unsaturated ring, and in the case of an unsaturated ring, it may be an aromatic ring. Preferably,
It is a saturated ring or an aromatic ring (heteroaromatic ring), and particularly preferably an aromatic ring (heteroaromatic ring). The nitrogen-containing heterocyclic group preferably has 0 to 60 carbon atoms, more preferably 1 to 50 carbon atoms,
3-40 is especially preferable. Further, as the ring-constituting atom,
Those selected from a nitrogen atom and a carbon atom are preferable, and in this case, the number of nitrogen atoms is preferably 1 or 2. As the nitrogen-containing heterocyclic group, for example, 1-pyrrolidinyl group, 1-pyrrolyl group, 2-pyrrolyl group, pyrrolyl group, imidazolyl group,
Examples thereof include a 1-imidazolyl group, a pyrazolyl group, a 3-, 4- or 5-pyrazolyl group, an indolizinyl group, a benzimidazolyl group, an indolinyl group, an indolyl group, a 2-indolyl group and a 3-indolyl group. Of these, 1
-Pyrrolyl group, 2-pyrrolyl group, pyrrolyl group, benzimidazolyl group, 1H-indazolyl group, indolinyl group, indolyl group, 2-indolyl group, 3-indolyl group are preferable, 2-pyrrolyl group, pyrrolyl group, indolinyl group, A 2-indolyl group and a 3-indolyl group are more preferable.

Examples of the substituent which the nitrogen-containing heterocyclic group may have include the substituents described for R1 in formula (I), and preferable substituents are an alkyl group, an aryl group, a carbamoyl group and a sulfamoyl group. A group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, and a cyano group.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent, which group has the same meaning as X in formula (I) and the preferred range is also the same.

Z represents a substituted aryl group, preferably having 6 to 60 carbon atoms, and examples of the substituent of the aryl group include the substituents in R1 of the general formula (I). Preferably, a halogen atom, an alkyl group, an aryl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group,
An acylamino group, a sulfonamide group, a sulfonyl group, an alkoxy group, and an aryloxy group. Z is a phenyl group substituted with a halogen atom or an alkoxy group at least at the 2-position (the phenyl group may further have a substituent at the 3- to 6-positions, and particularly may have a substituent at the 5-position). Preferred) is preferred. More preferably, it is a phenyl group having an alkoxy group at the 2-position and a substituent at the 5-position.

The coupler represented by the above general formula (Y-I) and preferably used in the present invention may form a dimer or higher multimer through Y and Z, or a polymer. It may be attached to a chain. Specific examples of the dye-forming coupler represented by formula (Y-I) and preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0111]

[Chemical 27]

[0112]

[Chemical 28]

[0113]

[Chemical 29]

[0114]

[Chemical 30]

[0115]

[Chemical 31]

[0116]

[Chemical 32]

[0117]

[Chemical 33]

[0118]

[Chemical 34]

[0119]

[Chemical 35]

[0120]

[Chemical 36]

The yellow dye-forming coupler used in other than the yellow image-forming layer and the yellow dye-forming coupler represented by the above general formula (I) or (II) used in the yellow image-forming layer are usually silver halide. In the emulsion layer, 1 × 10 ⁻³ to 1 mol per mol of silver halide,
Preferably, it can be used in the range of 1 × 10 ^-2 to 8 × 10 ^-1 mol. Further, the silver coating amount in the yellow image forming layer with respect to the coating amount of the yellow dye-forming coupler represented by the general formula (I) or (II) of the present invention is preferably 2 to 10 times in terms of molar amount, Preferably 3 times
6 times, most preferably 4 times to 6 times. Further, the yellow dye-forming coupler represented by the general formula (I) or (II) of the present invention is a magenta dye-forming coupler or a cyan dye-forming coupler for the purpose of adjusting other types of yellow dye-forming couplers or hues. It can also be used together. The magenta dye-forming coupler contained in the magenta image-forming layer of the present invention is a dye which can be used in a medium such as a high boiling point solvent so that the magenta image reacted with the developing agent of the present invention gives the spectral absorption of the present invention. Any forming coupler will do. Preferred magenta dye-forming couplers have the general formula (M):
Is a magenta dye-forming coupler represented by.

[0122]

[Chemical 37]

In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X is
It represents a hydrogen atom or a group capable of leaving by reacting with an oxidized product of a developing agent. The magenta dye-forming coupler represented by formula (M) is described in detail below. General formula (M)
The preferable skeleton among the dye-forming coupler skeletons represented by 1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] It is a triazole and is represented by the general formula (M-1) or the general formula (M-2), respectively.

[0124]

[Chemical 38]

In the formula, R ₁₁ and R ₁₂ represent a substituent, X
Represents a hydrogen atom or a group which is released by reacting with an oxidized product of a developing agent.

The substituents R ₁₁ in these general formulas,
R ₁₂ and X will be described in detail. Examples of R ₁₁ include the substituents listed for R 1 in the general formula (I).

Among the above, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group. The sulfamoyl group also includes those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group,
Examples thereof include ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group and sulfamoyl group. Of these substituents, preferred R
₁₁ is an alkyl group, an aryl group, an alkoxy group,
An aryloxy group is mentioned, and an alkyl group, an alkoxy group and an aryloxy group are more preferable.

R ₁₂ includes the substituents exemplified for R ₁₁ , and preferable substituents are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group and an aryloxy group. An alkyl group and a substituted aryl group are more preferable, and an alkyl group is the most preferable group, and a branched alkyl group is preferable among the alkyl groups. In the case of a branched alkyl group, it may be a substituted alkyl group. Examples of the substituent in this case include the substituents mentioned for R1 in the general formula (I).

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent. Examples of the group include the groups mentioned for X in the general formula (I).

The substituent of X is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5-membered or 6-membered nitrogen-containing heterocyclic group bonded with a nitrogen atom for coupling activity. ,
Particularly preferred is a halogen atom, a substituted aryloxy group, a substituted arylthio group, or a 1-pyrazolyl group. The most preferable X is a halogen atom, especially a chloro atom.

The above formulas (M-1) and (M-2) are used.
The dye-forming coupler used is R₁₁, R ₁₂Over the dimer
It may form the upper multimer and also binds to the polymer chain.
May be. Also, more preferred dye-forming couplers
Is a dye-forming coupler represented by the general formula (M-1).
It Represented by general formulas (M-1) and (M-2) below,
Specific examples of dye-forming couplers preferably used in the present invention
However, the present invention is not limited thereto.

[0132]

[Chemical Formula 39]

[0133]

[Chemical 40]

[0134]

[Chemical 41]

[0135]

[Chemical 42]

[0136]

[Chemical 43]

[0137]

[Chemical 44]

[0138]

[Chemical formula 45]

[0139]

[Chemical formula 46]

[0140]

[Chemical 47]

The magenta dye-forming coupler is usually used in the silver halide emulsion layer at a ratio of 1 per mol of silver halide.
× 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10
It can be used in the range of ^-1 mol. Further, the coating amount of silver in the magenta image forming layer with respect to the coating amount of the magenta dye forming coupler preferably used in the present invention is preferably 3 to 10 times, more preferably 4 times in terms of molar amount.
2 to 9 times, most preferably 5 to 8 times. The magenta dye-forming coupler preferably used in the present invention can also be used in combination with a cyan dye-forming coupler or a yellow dye-forming coupler for adjusting the hue of other types of magenta dye-forming couplers. In the present invention, it is particularly preferably used in combination with a yellow dye forming coupler. A yellow dye-forming coupler represented by the general formula (Y-I) which is preferably used in addition to the yellow image forming layer and a yellow represented by the general formula (I) or (II) of the present invention which is used in the yellow image forming layer. The dye-forming coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 mol, per mol of silver halide.
It can be used in the range of x10 ^-2 to 8 x 10 ^-1 mol. Preferred cyan dye-forming couplers are represented by formula (C1) and formula (C2).

[0142]

[Chemical 48]

In the formula, Za is --NH-- or --CH.
(R ₃₎ - represents, Zb and Zc each -C
Represents (R ₄ ) = or -N =. R ₁ , R ₂ and R
₃ represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.2 or more and 1.0 or less, respectively. However, R ₄ is
Represents a hydrogen atom or a substituent. However, two R in the formula
_{If four} are present, they may be the same or different. R ₅ and R ₆ represent a substituent, and R ₇ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent.

The present coupler will be described in detail below. The general formula (C1) of the present invention is specifically represented by the following general formulas (C3) to (C10).

[0145]

[Chemical 49]

In the formula, R _{1 to} R ₄ and X are represented by the general formula (C
It is synonymous with each of 1). Here,
In (C3) and (C7), a plurality of R ₄ may be the same or different.

In the present invention, the general formulas (C3) and (C
Cyan couplers represented by 4), (C5) and (C8) are preferable, and cyan couplers represented by (C4) are particularly preferable. In the general formula, the substituents represented by R ₁ , R ₂ and R ₃ have a Hammett's substituent constant σ _p value of 0.20.
The electron withdrawing group is 1.0 or more and 1.0 or less. Preferably, σ
It is an electron-withdrawing group having _ap value of 0.2 or more and 0.8 or less. Hammett's law was established in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
P. A rule of thumb proposed by Hammet, which is widely accepted today. Substituent constants obtained by the Hammett's rule include σ _p value and σ _m value, and these values are described in many general publications.
J. A. Dean, “Lange's Handbook of Chemistr”
y ”12th edition, 1979 (McGaw-Hill) and“ Special Issue on Chemistry ”, 122, 96-103 pages, 19
1979 (Nankodo) Chemical Review, 91, 165-195, 1991.

In the present invention, R ₁ , R ₂ and R ₃ are defined by Hammett's substituent constant values, which means that the values known from the literatures in these publications are limited to certain substituents. Of course, even if the value is unknown in the literature, it is included as long as it is included in the range when measured based on the Hammett's rule. σ _p value is 0.2 or more and 1.0
Specific examples of the following electron-withdrawing groups include an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Examples thereof include a carbamoyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an arylsulfonyl group. Among these substituents, the group capable of further having a substituent may further have a substituent as described for R1 in the general formula (I).

R ₁ , R ₂ and R ₃ are preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group or a sulfonyl group, more preferably a cyano group, an acyl group or an alkoxycarbonyl group. Group, an aryloxycarbonyl group, and a carbamoyl group. A preferred combination of R ₁ and R ₂ is when R ₁ is a cyano group and R ₂ is an alkoxycarbonyl group.

R ₄ represents a hydrogen atom or a substituent, and examples of the substituent include R in the general formula (I).
The substituents mentioned in 1 are mentioned.

Among the above, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group. The sulfamoyl group also includes those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group,
Examples thereof include ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group and sulfamoyl group.

Preferred examples of the substituent of R ₄ include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group and an acylamino group, more preferably an alkyl group and a substituted aryl group. A preferred group is a substituted aryl group. Examples of the substituent in this case include the substituents mentioned for R1 in the general formula (I).

In the cyan coupler represented by formula (C2), R ₅ and R ₆ represent a substituent, and the substituent represents a substituted or unsubstituted alkyl group or aryl group. Preferably, it represents a substituted aryl group, and examples of the substituent at this time include the substituents mentioned for R 1 in the general formula (I). R ₇ represents a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an alkoxy group, and an alkyl group. It is preferably a hydrogen atom.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent, and examples of the group include the groups mentioned for X in the general formula (I).

In formula (C1), the substituent of X is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an alkyl or arylthio group, and a nitrogen atom for the coupling activity. A 5-membered or 6-membered nitrogen-containing heterocyclic group to be bonded. Particularly preferred are a carbamoyloxy group and a substituted aryloxy group. The most preferable X is a carbamoyloxy group.

In formula (C2), the substituent of X is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group or a carbamoyloxy group, and a particularly preferable substituent is a halogen atom. Among them, it is a chlorine atom.

Represented by the above general formulas (C1) and (C2)
The dye-forming coupler is R₁, R₂, R ₃, R_Four, R_Five, R₆,
R₇It is possible to form multimers of dimers or more via
It may also be bound to a polymer chain. The general formula (C
1), represented by (C2), preferably used in the present invention
Specific examples of the dye-forming coupler will be shown below.
It is not limited to.

[0158]

[Chemical 50]

[0159]

[Chemical 51]

[0160]

[Chemical 52]

[0161]

[Chemical 53]

[0162]

[Chemical 54]

[0163]

[Chemical 55]

[0164]

[Chemical 56]

[0165]

[Chemical 57]

[0166]

[Chemical 58]

[0167]

[Chemical 59]

[0168]

[Chemical 60]

[0169]

[Chemical formula 61]

The cyan dye-forming coupler is usually used in the silver halide emulsion layer in an amount of 1 × per mol of silver halide.
10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹
It can be used in the molar range. Further, the coating amount of silver in the cyan image forming layer with respect to the coating amount of the cyan dye-forming coupler preferably used in the present invention is preferably 3 to 10 times, more preferably 4 to 10 times in terms of molar amount.
9 times, most preferably 5 times to 8 times. The cyan dye-forming coupler preferably used in the present invention is
It can also be used in combination with other types of cyan dye-forming couplers, yellow dye-forming couplers and magenta dye-forming couplers for hue adjustment and the like. General formula (I) of the present invention
Alternatively, in order to incorporate the dye-forming coupler represented by (II) into each of the dye-forming color light-sensitive materials described above, known techniques used in photographic useful substances such as ordinary dye-forming couplers can be applied. It is preferred that the dye-forming coupler is dissolved in a high-boiling organic solvent, optionally in combination with a low-boiling solvent, dispersed in the form of fine particles and added to the silver halide-containing layer. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, a wavelength adjusting agent, an aggregation preventing agent, a refractive index adjusting agent and the like may be used in combination.

The yellow, magenta and cyan image forming layers in the light-sensitive material of the present invention are laminated and coated on a support, but the order from the support may be any order. If necessary, an antihalation layer, an intermediate layer, a filter layer, a protective layer and the like can be arranged. When an oil-in-water emulsion dispersion method is used to add a dye-forming coupler or other organic compound to a light-sensitive material, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, and a low boiling point // Alternatively, a water-soluble organic solvent is also used in combination and dissolved, and then emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, or an ultrasonic disperser can be used. After or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. The high boiling point organic solvent preferably used in the present invention will be described below. The high boiling point organic solvent that can be used in the present invention is preferably the following general formulas [S-1] to [S-9].
Represented by

[0172]

[Chemical formula 62]

In the general formula [S-1], R ₁ , R ₂ and R
Each ₃ independently represents an aliphatic group or an aryl group. Further, a, b and c each independently represent 0 or 1. In the general formula [S-2], R ₄ and R ₅ each independently represent an aliphatic group or an aryl group, and R ₆ is a halogen atom (F, Cl, Br, I and below), alkyl group, alkoxy group, aryl Represents an oxy group, an alkoxycarbonyl group or an aryloxycarbonyl group,
d represents an integer of 0 to 3. When d is plural, plural R
₆ may be the same or different. In the general formula [S-3], Ar represents an aryl group, e represents an integer of 1 to 6, and R ₇ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond. General formula [S-4]
In, R ₈ represents an aliphatic group, f represents an integer of 1 to 6, and R ₉ represents a f-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond.

In the general formula [S-5], g represents an integer of 2 to 6, R ₁₀ represents a g-valent hydrocarbon group (excluding aryl group), and R ₁₁ represents an aliphatic group or an aryl group. Represent. In the general formula [S-6], R ₁₂ , R ₁₃ and R
Each ₁₄ independently represents a hydrogen atom, an aliphatic group or an aryl group. X is -CO- or -SO ₂ - represent.
R _{1 2} and R ₁₃ or R ₁₃ and R ₁₄ may bond to each other to form a ring. In formula [S-7], R ₁₅ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group, and R ₁₆ represents a halogen atom, an aliphatic group, It represents an aryl group, an alkoxy group or an aryloxy group, and h represents an integer of 0 to 3.
When h is plural, plural R ₁₆ may be the same or different.

In the general formula [S-8], R ₁₇ and R ₁₈ each independently represent an aliphatic group or an aryl group,
₁₉ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group, and i represents an integer of 0-4. When i is plural, plural R ₁₉ may be the same or different. R ₂₀ and R in the general formula [S-9]
₂₁ represents an aliphatic group or an aryl group. j represents 1 or 2.

Specific examples of the high boiling point organic solvent preferably used in the present invention are shown below.

[0177]

[Chemical formula 63]

[0178]

[Chemical 64]

[0179]

[Chemical 65]

[0180]

[Chemical formula 66]

[0181]

[Chemical formula 67]

[0182]

[Chemical 68]

[0183]

[Chemical 69]

[0184]

[Chemical 70]

[0185]

[Chemical 71]

[0186]

[Chemical 72]

[0187]

[Chemical formula 73]

[0188]

[Chemical 74]

The high boiling point solvent used in combination with the yellow dye forming coupler used in the yellow image forming layer of the invention is represented by the general formula [S-1], [S-4] or [S-5]. Compounds are preferred, and most preferred are compounds in which R ₁ , R ₂ , and R ₃ of the general formula [S-1] are aliphatic groups. The amount of the high-boiling organic solvent used is preferably 1 to 4 times, and more preferably 1 to 3 times the mass of the yellow dye-forming coupler. The high boiling point solvent used in combination with the magenta dye forming coupler used in the magenta image forming layer of the present invention is preferably a compound represented by the general formula [S-1], [S-4] or [S-5], and most preferably Are compounds in which R ₁ , R ₂ , and R ₃ of the general formula [S-1] are aliphatic groups. Further, the preferable amount of the high-boiling point organic solvent used is from 2 to 200 by mass based on the magenta dye-forming coupler.
It is preferably 5 times, more preferably 2.5 to 5 times.

The high boiling point solvent used in combination with the yellow dye forming coupler used in the cyan image forming layer of the present invention is preferably a compound represented by the general formula [S-1] to [S-5].
More preferred are general formula [S-1] and general formula [S-
5] compound. The amount of the high-boiling organic solvent used is preferably 1 to 5 times, and more preferably 2 to 4 times the mass of the coupler. Preferred compounds as the surfactant used for dispersing the photographic additives used in the light-sensitive material and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfo group or a salt thereof in one molecule. And the like. Specific examples thereof include A-1 to A-11 described in JP-A No. 64-26854. Further, a surfactant having a fluorine atom substituted in the alkyl group is also preferably used. These dispersions are usually
Although it is added to a coating solution containing a silver halide emulsion, it is preferable that the time from dispersion to addition to the coating solution and the time from addition to the coating solution and coating are short, both preferably within 10 hours. It is more preferably within 3 hours and within 20 minutes.

In the light-sensitive material, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or to a silver halide emulsion layer to fog. Is preferably improved. The compound for this purpose is preferably a hydroquinone derivative, more preferably 2,
It is a dialkyl hydroquinone such as 5-di-t-octyl hydroquinone. Particularly preferred compounds are the compounds represented by the general formula ii described in JP-A-4-133056, and the compounds II-1 to II described on pages 13 to 14 of the same.
The compound 1 described in -14 and 17 is mentioned.

It is also preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Benzotriazoles are mentioned as preferable ultraviolet absorbers, and particularly preferable compounds are those represented by the general formula III described in JP-A-1-250944.
-3, a compound represented by formula III described in JP-A-64-66646, and JP-A-63-187.
UV-1L to UV-27L described in No. 240, JP-A No. 4-4
Examples thereof include compounds represented by the general formula I described in JP-A-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is preferable that the light-sensitive material contains an oil-soluble dye or pigment because the white background is improved. Typical examples of oil-soluble dyes include compounds 1 to 27 described on pages (8) to (9) of JP-A-2-842. Gelatin is preferably used as a binder in the light-sensitive material. Especially, in order to remove the coloring component of gelatin, the gelatin extract is treated with hydrogen peroxide, or the raw material ossein is extracted with hydrogen peroxide, or it is produced from uncolored raw bone. It is preferable to use gelatin whose transmittance is improved by using The gelatin may be any of alkali-treated ossein gelatin, acid-treated gelatin, gelatin derivative and modified gelatin, but alkali-treated ossein gelatin is particularly preferable.

The transmittance of gelatin was 7% when a 10% solution was prepared and the transmittance was measured with a spectrophotometer at 420 nm.
It is preferably 0% or more. The jelly strength of gelatin (by the Paggy method) is preferably 250 or more,
It is particularly preferably 270 or more. The ratio of gelatin to the total coating binder is not particularly limited, but it is preferable to use a large ratio, specifically at least 20-
A preferable effect can be obtained by using it at a ratio of 100%.

The total amount of gelatin contained on the image forming surface side of the light-sensitive material of the present invention is preferably less than 11 g / m ² . The lower limit is not particularly limited, but generally 3.0 g / m ² or more is preferable from the viewpoint of physical properties or photographic performance. The amount of gelatin is determined by converting it to the mass of gelatin containing 11.0% of water by the water content measuring method described in the Paggy method.

As the binder hardener typified by gelatin, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination.
Specifically, JP-A-61-249054 and 61-24
It is preferable to use the compounds described in No. 5153 and the like. Further, in order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storability, JP-A-3-15764 is used in the colloid layer.
It is preferable to add an antiseptic and an antifungal agent as described in No. 6.

The color developer used in the present invention is described below. Although the color developing composition of the present invention contains a color developing agent, a known aromatic primary amine color developing agent is preferable, and a p-phenylenediamine derivative is particularly preferable. Among these p-phenylenediamine derivatives, preferred compounds can be represented by the following general formula (D). General formula (D)

[0198]

[Chemical 75]

In the general formula (D), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, and R ₁ and R ₂
May be the same or different, and R ₁ and R ₂ may combine with each other to form a ring. R ₃ represents a substituent. The substituted or unsubstituted alkyl group for R ₁ and R ₂ preferably has 1 to 15 carbon atoms, and more preferably 1 to 15 carbon atoms.
It is 10, and most preferably has 1 to 6 carbon atoms, and examples of the unsubstituted alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and pentadecyl. The substituent of the substituted alkyl group is R ₁₂ in formula (M-1).
Substituents. What is preferably used in the present invention is _one in which _one of R ₁ and R ₂ has a water-soluble group.

Specific examples of the water-soluble group include-(CH ₂ ) _{n
-CH 2 OH, - (CH 2} ) n -NHSO 2 - (CH 2) n -
_{CH 3, - (CH 2)} n -O- (CH 2) n -CH 3, - (C
In _{H 2 CH 2 O) n -C} m H 2m + 1 ( wherein, m and n represent an integer of 0 or more, respectively), -. CO ₂ H group, and as -SO ₃ H group and the like . Examples of the substituent of R ₃ include the substituents of R _{1 in} the general formula (I). Among R ₃ , preferred groups are a substituted or unsubstituted alkyl group, an alkoxy group, an alkylthio group and an acylamino group, more preferably a substituted or unsubstituted alkyl group, and most preferably an unsubstituted alkyl group. Among the substituents of R _3, the group having a carbon atom in the partial structure preferably has a total carbon number of 1 to 15, and more preferably 1 to 1.
0, more preferably 1 to 6, most preferably 1 to 3. The most preferred substituent for R ₃ is methyl. The compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

N-1) N, N-diethyl-p-phenylenediamine N-2) 4-amino-N, N-diethyl-3-methylaniline N-3) 4-amino-N- (β-hydroxyethyl) )
-N-methylaniline N-4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline N-5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methyl Aniline N-6) 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline N-7) 4-Amino-N-ethyl-N- (4-hydroxybutyl) -3-methyl Aniline N-8) 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline N-9) 4-amino-N, N-diethyl-3- (β-
Hydroxyethyl) aniline N-10) 4-amino-N-ethyl-N- (β-methoxyethyl) -3-methylaniline N-11) 4-amino-N- (β-ethoxyethyl)
-N-ethyl-3-methylaniline N-12) 4-amino-N- (3-carbamoylpropyl) -Nn-propyl-3-methylaniline N-13) 4-amino-N- (4-carbamoyl) Butyl) -N-n-propyl-3-methylaniline N-14) N- (4-amino-3-methylphenyl)
-3-Hydroxypyrrolidine N-15) N- (4-amino-3-methylphenyl)
-3-Hydroxymethylpyrrolidine N-16) N- (4-amino-3-methylphenyl)
-3-Pyrrolidine carboxamide

Of these, the compounds represented by the above-mentioned general formula (D) are particularly preferred for use in the present invention. Among them, the exemplified compounds N-5), N-6) and N-
7), N-8) and N-12) are preferable, N-5) and N-8) are more preferable, and N-8) is the most preferable.

The compounds represented by formula (D) used in the present invention are described in J. Am. Chem. Soc. (Journal of America Chemical Society) 7
It can be synthesized according to the method described in Volume 3, page 3100.

General formula (D) out of all developing agents in the developing solution
The content of the compound represented by is preferably 55 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and most preferably 9 mol% or more.
It is 0 mol% or more. The amount of the p-phenylenediamine-based color developing agent added to the color developing solution is preferably 0.5 × 10 ⁻² mol or more, and more preferably 1.0 × 10 ⁻² to 1 liter of the color developing solution. It is in the range of 1.0 × 10 ^-1 mol, more preferably 1.5 × 10 ^{-2 to} 5.
It is in the range of 0 × 10 ^-2 mol.

To the color developing solution applied to the processing of the light-sensitive material of the present invention, known developing solution component compounds can be added in addition to the above-mentioned primary aromatic amino color developing agent. For example, an alkali agent such as sodium hydroxide, sodium carbonate or potassium carbonate, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickener may be optionally contained. it can.

The pH value of the color developing solution is usually 7 or more, and most commonly about 10 to about 13. The color development temperature is usually 15 ° C or higher, generally 20 ° C to 50 ° C.
Is the range. For rapid processing, it is preferable to carry out at 30 ° C or higher. The color development time is generally preferably in the range of 20 seconds to 180 seconds, more preferably 30 seconds to 150 seconds. The light-sensitive material of the present invention may contain these color developing agents as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and may be processed with an alkaline activating bath.

Further, these p-phenylenediamine derivatives include, in addition to the salts exemplified above, sulfates, hydrochlorides and p-phenylene diamines.
-A salt such as a toluene sulfonate may be used or may not be formed.

Further, these p-phenylenediamine derivatives may be salts such as sulfuric acid hydrochloride, hydrochloride and p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 per liter of the developing solution.
g, more preferably about 0.5 g to about 10 g. The color developer used in the present invention is preferably p
H9 to 12, more preferably 9 to 11.0, and the color developing solution can contain other known compounds as developing solution components. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, tetraborate Sodium (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate),
Examples thereof include potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
The amount of the buffer added to the color developer is 0.1 mol / l.
It is preferably not less than 0.1 mol / l to 0.
It is particularly preferably 4 mol / l. In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited to these. -Nitrilotriacetic acid-Diethylenetriaminepentaacetic acid-Ethylenediaminetetraacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1,3 -Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenyl Acetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid Chelating agent is required You may use together 2 or more types as needed. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter. If necessary, any development accelerator can be added to the color developing solution.

As a development accelerator, Japanese Patent Publication No. 37-160
88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247, and the like. 49829 and 50-1555.
No. 4, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30074.
No. 5, JP-A-56-156826 and JP-A-52-4342.
9, quaternary ammonium salts, p-aminophenols described in US Pat. Nos. 2,610,122 and 4,119,462, and US Pat.
No. 903, No. 3,128,182, No. 4,230,7
No. 96, No. 3,253,919, Japanese Patent Publication No. 41-114
31, U.S. Pat. Nos. 2,482,546 and 2,59
Amine compounds described in 6,926 and 3,582,346, etc., JP-B-37-16088, 42-2.
5201, U.S. Pat. No. 3,128,183, Japanese Patent Publication Nos. 41-11431, 42-23883, and U.S. Pat. No. 3,532,501, and the like, and other 1-phenyl-3-phenylalkylene oxides. Pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary. In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used.
Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine. The color developer used in the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4′-diamino-2,2′-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / l, preferably 0.1 to 4 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added. The processing temperature of the color developing solution of the present invention is 20 to 50 ° C., preferably 30 to 50 ° C.
40 ° C. Treatment time is 20 seconds to 5 minutes, preferably 3
It is 0 seconds to 2 minutes. It is preferable that the replenishment amount is small, but ^{20 to} 600 ml, preferably 50 to 600 ml per 1 m ^{2 of} the light-sensitive material.
It is 300 ml. More preferably 100 ml to 200
ml. Next, the bleach-fixing solution used in the present invention will be described. As the bleaching agent used in the bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular, organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, Aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid and the like) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferable. Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. The aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,
3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
Methyliminodiacetic acid, iminodiacetic acid, glycol ether diamine tetraacetic acid, etc. can be mentioned. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and an iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and phosphoric acid. Second
A ferric ion complex salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid. In addition, the chelating agent may be used in excess of the amount required to form the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol /
1 is preferably 0.05 to 0.50 mol / l.

In the bleach-fixing solution, various compounds as bleaching accelerators can be used in addition to the halide ion of the present invention. For example, US Pat. No. 3,893,85
No. 8, German Patent No. 1,290,812, JP-A No. 53-95630, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond. And Japanese Examined Patent Publication No. Sho 45-8506 and Japanese Patent Laid-Open No. Sho 52-2083.
2, No. 53-32735, and U.S. Pat. No. 3,706,5.
The thiourea compounds described in No. 61 and the like are preferable because of their excellent bleaching power. In addition, in the bleach-fixing solution used in the present invention, if necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate,
Phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and other inorganic acids, organic acids and their alkali metal or ammonium salts having pH buffering ability, or corrosion inhibitors such as ammonium nitrate and guanidine Etc. can be added.

The fixing agents used in the bleach-fixing solution according to the present invention are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-
It is a water-soluble silver halide solubilizer such as thioether compounds such as 1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per 1 l is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. PH of bleach-fix solution
The area is preferably from 3 to 10, more preferably from 5 to 9. Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol. The bleach-fixing solution in the present invention contains a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative. ), Metabisulfite (eg, potassium metabisulfite, sodium methylbisulfite, ammonium metabisulfite, etc.) and the like. These compounds are converted to sulfite ions to about 0.02
The content is preferably 0.50 mol / l, and more preferably 0.04 to 0.40 mol / l. As a preservative, it is common to add sulfite, but in addition, ascorbic acid, carbonyl bisulfite adduct, or
A carbonyl compound or the like may be added. Further buffer,
You may add it as needed to a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent, etc.

The shorter the processing time of the desilvering step in the present invention, the more remarkable the effect of the present invention, and the desilvering step time is 2 minutes or less, more preferably 1 minute or less. The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as bleach-fixing. The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set. this house,
The relationship between the number of washing tanks and the amount of water in the multi-stage counterflow system is described in the Journal of the Society of Motion,
Picture and Television Engineers (Journalof the Society of
Motion Picture and Televi
sion Engineers) Vol. 64, p. 248
~ 253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 4.

According to the multi-stage countercurrent system, the amount of washing water can be greatly reduced, for example, 1 l or less, preferably 0.5 l or less per 1 m ^{2 of the} light-sensitive material is possible, and the effect of the present invention is remarkable, but the tank Due to an increase in the residence time of water inside the bacteria, there is a problem in that bacteria propagate and the floating substances formed adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, Japanese Patent Application No. 61-131
The method of reducing calcium and magnesium described in No. 632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based germicides such as chlorinated sodium isocyanurate described in JP-A-61-212045, and JP-A-60-105487. Benzotriazole, copper ion and others by Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents", Hygiene Technology Association "Sterilization, Sterilization and Antifungal Technology of Microorganisms", Japan Society for Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" It is also possible to use the bactericide described in. Furthermore, a surfactant as a draining agent and a chelating agent typified by EDTA can be used as a softening agent for the washing water.

It is also possible to carry out the treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting a film pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used. Further, a surfactant, a fluorescent whitening agent, and a hardener can be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a washing step, JP-A-57-8 is used.
No. 543, No. 58-14834, No. 60-22034.
All known methods described in No. 5, etc. can be used.

In addition, 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound. In addition, the stabilizing solution can be drastically reduced (1 liter or less, more preferably 0.5 liter or less) by adopting a multi-stage countercurrent system like the washing water. Replenishment of washing water or stabilizing solution may be continuous or intermittent. In the latter case, the processing is performed according to the processing amount or at regular time intervals. The pH of the washing step or stabilizing step of the present invention is 4 to 10, preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 15 to 45 ° C, preferably 20 to 40 ° C. Although the time can be set arbitrarily, the effect of the present invention is more remarkable when the time is short, and is preferably 30 seconds to 2 minutes, more preferably 30 seconds to 1 minute 30 seconds. The smaller the replenishment amount, the more preferable from the viewpoints of running cost, reduction of discharge amount, handleability, and the like, and the effect of the present invention is great.

The specific amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount per unit area from the pre-bath. The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by causing the overflow of washing water reduced by the multi-stage countercurrent system to flow into the bleach-fixing bath of the preceding bath and replenishing the bleach-fixing bath with a concentrated liquid. In the present invention, the total time of the bleach-fixing step and the washing or stabilizing step is preferably 3 minutes or less.

In the present invention, the inclusion of bromide ion or iodide ion in the bleach-fixing solution prevents image unevenness which may occur when the solution enters the bleach-fixing solution from the developing solution, and provides high-quality halftone dots. It is very good at obtaining images. The preferable addition amount of bromide ion is 1 × 10 ⁻² to 2 mol per liter, and the preferable addition amount of iodide ion is 5 × 10 ^{−4 to} 5 × 10 ⁻² mol. Particularly preferred is 1/10 to 1 mol of bromide ion.

In the present invention, when the linear velocity of processing is high, the processing per short time increases and the productivity is improved, while the processing machine becomes large, and when the linear velocity is low, the processing machine can be downsized but the productivity is low. . Therefore, in the present invention, the linear velocity of the treatment is preferably 1 cm to 90 cm per second, more preferably 3 cm to 20 cm per second, and most preferably 5 cm to 10 cm per second.

Next, a method of exposing the above-mentioned silver halide color light-sensitive material will be described. In the present invention, substantially the maximum density of each photosensitive layer is used without using the density of the gradation portion,
Is the characteristic curve in continuous gradation, not the gradation part,
The maximum density of each light-sensitive layer is used, and the substantially maximum density is less than the exposure amount at which the point γ becomes 0.3 in the part where the maximum color density is reached from the gradation part through the shoulder part. High light intensity of 1 logE or more (preferably point γ
0.1logE-0.5l than the exposure amount that makes 0.3
ogE is a density at a point of high light amount). Also, the line width is 30
It is preferable that a fine line having a diameter of 30 μm or less can be drawn if the line width is 30 μm when exposed to light having a beam diameter of 30 μm.
It is to be able to draw fine lines of m or less. In the image forming method of the present invention, the exposure time is 10 ^-2 to 10 ^-9 seconds (preferably 10 ^-3 to 10 ^-9 seconds), and the exposure is performed at least three times on the same photosensitive layer. It is characterized by Particularly preferably, the exposure time is 10 ^-4 to 10 ^-8 seconds, and when the exposure time is 10 ^-5 to 10 ^-8 seconds, it is preferable to perform at least 8 exposures. The light source may be any gas laser, solid-state laser (LD), LED (inorganic or organic), spot-focused Xe light source, etc., but a solid-state laser or LED is particularly preferable. The light source needs to be spectrally divided into the color-sensing wavelengths of the respective dye-forming layers. For this purpose, an appropriate color filter (containing a dye,
It is preferable to select and use the oscillation wavelength of LD or LED). Further, both may be used in combination. The spot diameter of the light source is not particularly limited,
The half-width of light intensity is preferably 0.5 to 50 μm, and 5
To 50 μm are more preferable, and especially 5 to 30 μm
m is preferred. The shape of the spot may be circular, elliptical or rectangular. The light intensity distribution of one spot may be a Gaussian distribution or a trapezoid with a relatively constant intensity. In particular, one light source may be used, but an array in which a plurality of light sources are arranged is preferable.

In the present invention, the exposure is generally performed by scanning exposure, and the light source may be scanned or the photosensitive material may be scanned. Alternatively, both of them may be scanned. One exposure time is defined by the following formula. Exposure time = spot diameter /
Moving speed of light source (or moving speed of photosensitive material)
The spot diameter is the diameter (half-width, unit: μm) of the spot in the direction in which the light source used for scanning exposure moves during exposure. The moving speed of the light source is the speed at which the light source used for scanning exposure moves per unit time (unit: μm /
Second). In general, the spot diameter does not have to be the same as the pixel diameter, and may be larger or smaller than that. The number of times of exposure referred to in the present invention is the number of times of irradiation of light with which the same color-sensitive layer is sensed for one point (pixel) on the photosensitive material. On the other hand, 1
The number of exposures with an intensity of / 5 or more. Therefore, exposures less than 1/5, stray light, and overlap between spots are not included in the number of times. Furthermore, the number of times of giving a strength of 1/2 or more is 3 times or more,
In particular, it is preferably 8 times or more.

The image forming method preferably used will be described below in detail including a system preferable for the method.

As the system, the photosensitive material is automatically pulled out from the magazine, cut into sheets, wound around the outer drum for exposure and rotated, and halftone dot image information is emitted from three or more light sources having different wavelengths. 8 units each
Scanning exposure is performed by using an exposure ray light source that is a combination of two or more pieces, and a halftone dot image of area gradation is recorded by dots having a resolution of 2000 dpi or more, and then the exposed color photosensitive material is automatically processed by an automatic processor. A direct digital color proof system and an image forming method for developing and outputting a halftone dot color proof image are preferable.
Among them, preferably B1 size or more, more preferably A
A color proof photosensitive material, system, and image forming method suitable for outputting a halftone dot color proof image of three or more sizes are preferable, but not limited thereto.

The preferable color proof light-sensitive material, system and image forming method of the present invention are described below, but the invention is not limited thereto. Resolution of 2400 dpi or higher, 1-dot exposure beam diameter is 0.5 at half-value width of light intensity
At least one exposure light source exposes one dot at an exposure time of 10 ^-8 seconds or more and 10 ^-2 seconds or less, and the rotation number of the outer drum is 1 μm or more and 50 μm or more.
00 rpm or more and 4000 rpm or less, the wavelength of at least one exposure light source is 700 nm or more, the exposure amount of at least one exposure light source is two stages or more, the exposure energy of the longest exposure light source is other exposure 1.1 times or more of energy, after exposure,
The photosensitive material should be peeled from the outer drum and conveyed so that the exposed surface faces downward, and the emulsion surface should be turned downward in the color developer, bleach-fix solution and washing bath of an automatic processor. The time from the end of exposure of the light-sensitive material to the tip of the color developing solution being within 20 seconds or more and 3 minutes or less, and from the end of exposure to the color development of the exposed light-sensitive material at the beginning. The difference between the time to enter the solution and the time to transfer the rear end in the transport direction to the color developing solution is 1 minute or more and 10 minutes or less, and the processing time of the color developing solution and the bleach-fixing solution is 10 seconds or more and 100 seconds or less. And the difference in processing time is within 30 seconds, the capacity of the processing tank for the color developing solution and the bleach-fixing solution is 8 L or more and 20 L or less, and the washing tank is 2 tanks or more and 5 tanks or less. When supplied by the color color development and bleach-fixing solution are integrated kit, and replenishment amount is per photosensitive material 1m ² color color development, in 50ml or 300ml or less, and replenishment amount of bleach-fixing solution is light-sensitive material 1m 30ml to 250ml per ² and the replenishment amount of the wash water is 50ml to 1000ml in the whole wash water
The following, and automatically replenishing the area of the light-sensitive material to be processed, the automatic developing machine has a mechanism in which at least one aerial turn conveying roller is automatically washed, an emulsion of the light-sensitive material At least one of the guide plates contacting the surface uses Teflon (registered trademark) material, during proof printing or for another output printing,
By writing a specific image and measuring the image density or chromaticity or visually comparing it with the target image, the sensitivity of the photosensitive material between lots, changes over time, changes in temperature and humidity during exposure, and changes in the processing liquid state can be evaluated. Has a calibration function to correct changes, and Dmax of the photosensitive material
Having a function to perform calibration with a continuous tone image having a lower density than that, capable of performing a calibration by visually determining 20% or more and 80% or less of a halftone dot image or density measurement or color difference colorimetry, and two or more The same size photosensitive material is supplied in a magazine, and when the photosensitive material in one magazine is exhausted, the photosensitive material in the other magazine is automatically supplied. It is supplied at the same time, and the size is automatically changed. The length of one photosensitive material is 30m or more and 100m or less. It takes 10 seconds or more until the photosensitive material is pulled out from the magazine and the exposure is started after the pulling out. Within 100 seconds, black plate image is formed from yellow, magenta, and cyan, black plate mesh The difference in dot gain of each color forming the film is 5% or less, the total thickness of the support used for the photosensitive material is 50 μm or more and 150 μm, and the thickness of the surface laminate of the support used for the photosensitive material is 10 μm or more. 50 μm, the thickness of the back laminate of the support used for the light-sensitive material is 10 μm or more and 50 μm, and 0.1 μm or more and 30 μm or less on the surface opposite to the surface of the light-sensitive material coated with the photosensitive layer. Of the photosensitive material, the total thickness of the surface of the photosensitive material having the photosensitive silver halide is 3 μm or more and 30 μm or less, the total thickness of the surface of the photosensitive material having the photosensitive silver halide and the back surface of the photosensitive material. The difference in total film thickness is 10 μm or less, the silver chloride content of the photosensitive silver halide used in the light-sensitive material is 90% or more, and the emulsion surface of the light-sensitive material is outside. Used in the form of a roll toward, the peak wavelength of the maximum spectral sensitivity of at least one layer is 700nm or more, and the photosensitive material cut into a sheet by a squeeze roller is automatically transferred to a drum. The present invention can be applied to a direct digital color proof system, an image forming method, and a color proof light-sensitive material having one or a plurality of features selected from features such as winding.

The shape of the spot is circular, elliptical,
Any of rectangular shapes may be used. The light intensity distribution of one spot may be a Gaussian distribution or a trapezoid with a relatively constant intensity. In particular, one light source may be used, but a multi-channel array in which a plurality of light sources of the same wavelength (preferably 10 to 100, more preferably 40 to 80) are arranged is preferable. Regarding an exposure method and an image forming method using a laser, an LED and an array thereof as a light source, JP-A-10-142752 and JP-A-11-2
No. 42315, JP-A 2000-147723, JP-A 2
000-246958, JP-A-2000-354174.
No. 2000-206654, European Patent EP-1
It is described in detail in No. 048976A and the like and can be preferably used in the present invention.

More specifically, it is as follows. A preferred embodiment of the exposure light source is JP-A 2000-147.
No. 723 of Japanese Patent Laid-Open No. 723 or JP 2000-2066.
No. 54, paragraph numbers 0053, 0059 to 0061, 00
64 to 0067 and are preferably applied to the present invention. Preferable modes of the beam of the exposure light source and the array of the exposure light source are described in paragraph Nos. 0022 to 0023 of JP-A-2000-147723 and JP-A-2000-206.
No. 654 to paragraphs 0025 to 0030, which are preferably applied to the present invention. In order to improve the productivity at the time of exposure, a method of winding a photosensitive material around a drum and performing scanning exposure is excellent. The aspect of the preferable light source is
An LED array described in JP-A-2000-246958, and JP-A-2000-2469 having the LED array.
The image recording apparatus described in No. 58 is preferably applied according to the present invention. Regarding the method of winding the drum, it is described in paragraph Nos. 0057 to 00 of JP-A-2000-206654.
58, 0062 to 0063, and likewise preferably applied to the present invention.

Further, it is also preferable to perform calibration by the method described in European Patent EP-1048976A to stably form an image, which is applied to the present invention. Regarding the method for converting digital image data into image data for exposure and the exposure processing method, which is preferably adopted in the present invention for producing a color proof, there is disclosed in JP-A-2000-3.
The materials described in JP-A No. 54174 and JP-A No. 2000-147723 can be used as they are. More specifically,
1 is a color proof manufacturing apparatus of FIG. 1 described in Japanese Patent Application Laid-Open No. 2000-354174, including FIG. 1 and FIG. The described portions of 0034 to 0057 are preferably incorporated as part of the specification of the present invention.

[0230]

The present invention will be described in more detail based on the following examples. Example 1 Paper support laminated on both sides with polyethylene (107 μ
m) (base paper basis weight 81 g / m ² front polyethylene laminate 15 μm back polyethylene laminate 13 μm total thickness 107 μm) After corona discharge treatment on the front side, a gelatin undercoat layer containing sodium dodecylbenzene sulfonate was provided, and further various A photographic constituent layer was applied to prepare a sample 001 having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Third Layer Coating Solution Yellow coupler (ExY-1) 600 g, cyan coupler (ExC-2) 2 g, color mixture inhibitor (Cpd-4) 2
0 g, 40 g of color image stabilizer (Cpd-11), and 40 g of color image stabilizer (Cpd-12) were added to a high-boiling organic solvent (Sol
v-3) 300 g, high boiling organic solvent (Solv-4) 6
00g, high-boiling organic solvent (Solv-5) 300g and ethyl acetate 700ml were dissolved in 80% surfactant (W-3) 80g emulsified and dispersed in 5000% 20% gelatin, and then water was added to make the total amount. To prepare 12,000 g of an emulsified dispersion A. On the other hand, silver chlorobromide emulsion G (cubic, average grain size 0.60 μm, variation coefficient of grain size distribution is 0.10, and 0.3 mol% of silver bromide is a part of grain surface based on silver chloride). Was locally contained in.) Was prepared. a) Blue-sensitive emulsion In this emulsion, the sensitizing dyes A and C were 0.50 × 10 −4 mol per mol of silver halide, and the sensitizing dye B was 4.1 × per mol of silver halide. 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion G were mixed to prepare a coating solution for the third layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

-Preparation of coating solutions for the first layer, the second layer and the fourth to eighth layers-The coating solutions for the first layer, the second layer and the fourth to seventh layers are also the third layer coating solutions. Prepared in a similar manner. As the gelatin hardener for each layer, H-1, H-2 and H-3 represented by the following formula were used. In addition, Ab-1, Ab-2, Ab-3 and Ab-4
Respectively, the total amount is 15.0 mg / m ² , 60.0 mg / m ² ,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0233]

[Chemical 76]

[0234]

[Chemical 77]

For the silver chlorobromide emulsion in each photosensitive emulsion layer, the indicated amount of the spectral sensitizing dye and the optimum amount of the crystal habit controlling agent 1 shown below were used, respectively.

[0236]

[Chemical 78]

B) Green-sensitive emulsion

[0238]

[Chemical 79]

Sensitizing dye D was added per mol of silver halide,
3.6 × 10 ^-4 mol, sensitizing dye E was 7.0 × 10 ^-5 mol per mol of silver halide, and sensitizing dye F was 2.8 × 10 4.
^-4 mol was added. For the chemical ripening of this emulsion, a sulfur sensitizer and a gold sensitizer were added. c) Red-sensitive emulsion

[0240]

[Chemical 80]

Sensitizing dyes G and H were added in an amount of 1.1 × 10 ^-4 mol per mol of silver halide. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. For the chemical ripening of this emulsion, a sulfur sensitizer and a gold sensitizer were added.

[0242]

[Chemical 81]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (3-methylureidophenyl) -5-
Mercaptotetrazole was added to 3.3 × 10 ⁻⁴ , 1.0 × 10 ⁻³ , and 3.0 × per mol of silver halide, respectively.
10 ⁻⁴ mol was added. Further, further, 3.0 mg / m ² and 0.2 mg / m ² respectively in the first layer, the fourth layer, the fifth layer, and the sixth layer.
m ² , 0.2 mg / m ² , and 0.2 mg / m ² were additionally added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added at 1 × 10 ⁻⁴ and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

Catechol-3,5-in the fourth and sixth layers
Disodium disulfonate, 44 mg / m ² and 3, respectively
9 mg / m ² was added in each.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support polyethylene laminated paper [white pigment on the first layer side (TiO ₂ content 1
7% by mass). The whiteness on the first layer side is L * = 96.
5, a * = 0.1, b * = 0.8. ]

[0247] First layer (anti-halation layer)      Black colloidal silver 0.11      Gelatin 1.04      Color mixing inhibitor (Cpd-1) 0.047      Color image stabilizer (Cpd-2) 0.003      Color image stabilizer (Cpd-3) 0.030      Color mixing inhibitor (Cpd-4) 0.003      High boiling organic solvent (Solv-1) 0.044      High boiling organic solvent (Solv-2) 0.077

[0248] Second layer (middle layer)      Gelatin 1.40      Irradiation prevention dye (AI) 0.007      Irradiation prevention dye (A-II) 0.004 Third layer (blue sensitive emulsion layer)       Silver chlorobromide emulsion G     (Cube, average particle size 0.60 μm, coefficient of variation of particle size distribution       0.10, and 0.3 mol% of silver bromide was added to the surface of grains based on silver chloride.       It was partially contained locally. )                   (As silver) 0.26      Gelatin 1.19      Yellow coupler (ExY-1) 0.34      Cyan coupler (ExC-2) 0.001      High boiling organic solvent (Solv-4) 0.34      High boiling organic solvent (Solv-5) 0.34      Color mixing inhibitor (Cpd-4) 0.01      Color image stabilizer (Cpd-11) 0.02      Color image stabilizer (Cpd-12) 0.02

[0249] Fourth layer (color mixing prevention layer)      Gelatin 1.04      Color mixing inhibitor (Cpd-1) 0.13      Color image stabilizer (Cpd-2) 0.008      Color image stabilizer (Cpd-3) 0.10      Color mixing inhibitor (Cpd-4) 0.009      High boiling organic solvent (Solv-1) 0.13      High boiling organic solvent (Solv-2) 0.22      Irradiation prevention dye (A-III) 0.003      Irradiation prevention dye (A-IV) 0.011 Fifth layer (green sensitive emulsion layer)      Silver chlorobromide emulsion H     (Cube, average particle size 0.39 μm, coefficient of variation of particle size distribution       0.08 each. For each size emulsion 0.7 mol% silver bromide and silver chloride       It was locally contained on a part of the surface of the particle serving as a base. )                   0.25 (as silver)      Gelatin 1.24      Magenta coupler (ExM-1) 0.11      Yellow coupler (ExY-2) 0.05      High boiling organic solvent (Solv-3) 0.40      Color mixing inhibitor (Cpd-1) 0.02      Color image stabilizer (Cpd-9) 0.014      Color image stabilizer (Cpd-10) 0.023      Color image stabilizer (Cpd-8) 0.04      Color image stabilizer (Cpd-11) 0.004      Color mixing inhibitor (Cpd-4) 0.02      Color image stabilizer (Cpd-3) 0.045      UV absorber (UV-1) 0.01      UV absorber (UV-2) 0.05      UV absorber (UV-3) 0.06      Additive (Cpd-14) 0.001

[0250] Sixth layer (color mixing prevention layer)      Gelatin 0.91      Color mixing inhibitor (Cpd-1) 0.12      Color image stabilizer (Cpd-2) 0.007      Color image stabilizer (Cpd-3) 0.07      Color mixing inhibitor (Cpd-4) 0.008      High boiling organic solvent (Solv-1) 0.12      High boiling organic solvent (Solv-2) 0.19      Irradiation prevention dye (A-III) 0.002      Irradiation prevention dye (A-IV) 0.010

[0251] Seventh layer (red sensitive emulsion layer)      Silver chlorobromide emulsion I     (Cube, average particle size 0.50 μm, coefficient of variation of particle size distribution       0.09 and 0.8 mol% of silver bromide on the surface of grains based on silver chloride.       It was partially contained locally. )                     (As silver) 0.19      Gelatin 0.76      Cyan coupler (ExC-1) 0.11      High boiling organic solvent (Solv-6) 0.16      Color image stabilizer (Cpd-3) 0.03      Color image stabilizer (Cpd-5) 0.05      Color image stabilizer (Cpd-6) 0.05      Color image stabilizer (Cpd-7) 0.01      Color image stabilizer (Cpd-13) 0.01      Color image stabilizer (Cpd-8) 0.02      Color mixing inhibitor (Cpd-4) 0.02      Ultraviolet absorber (UV-2) 0.04      UV absorber (UV-3) 0.13      Color mixing inhibitor (Cpd-1) 0.03

[0252] Eighth layer (protection layer)      Acid-treated gelatin 1.67      Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%)                                                         0.04      Polymethylmethacrylate 0.05      Surfactant (W-1) 0.009      Surfactant (W-2) 0.009

[0253] First layer on back (protective layer)     Gelatin 5.5 Second layer on back side (protective layer)     Gelatin 1.2     Polymethylmethacrylate 0.05

The compounds used are shown below.

[0255]

[Chemical formula 82]

[0256]

[Chemical 83]

[0257]

[Chemical 84]

[0258]

[Chemical 85]

[0259]

[Chemical 86]

[0260]

[Chemical 87]

[0261]

[Chemical 88]

[0262]

[Chemical 89]

[0263]

[Chemical 90]

With respect to the sample 001 obtained as described above, the sample 0 was obtained except that the constitution of the third layer was changed as follows.
Sample 002 was prepared in exactly the same manner as 01. In addition,
The numbers represent the coating amount (g / m ² ), and the halogenated emulsion amount represents the coating amount in terms of silver.

[0265] (Structure of the third layer of sample 002)       Silver chlorobromide emulsion G (same emulsion as sample 001)                   (As silver) 0.18      Gelatin 1.19      Yellow coupler (Exemplified compound (3)) 0.29      Cyan coupler (ExC-2) 0.001      High boiling organic solvent (Solv-4) 0.50      High boiling organic solvent (Solv-5) 0.14      Color mixing inhibitor (Cpd-4) 0.01      Color image stabilizer (Cpd-11) 0.02      Color image stabilizer (Cpd-12) 0.02

Samples 001 and 002 obtained as described above were suction-adhered to and wound on a rotating drum having a diameter of 30 cm, rotated at 270 rpm, and rotated at R (699 nm), G
(525 nm), B (465 nm) LED array (L
The number of EDs was 64 each, and exposure was performed using light. Each light source was a spot having a trapezoidal intensity distribution and a width of 30 μm, and the exposure time per beam was 30 μsec. Multiple exposure was performed by shifting the beams by 10 μm so that the overlapping of the exposure beams on the photosensitive surface of the photosensitive material was 20 μm. After exposure, color development processing was performed according to the following processing steps.

Treatment process Temperature Time Replenishment amount * Tank capacity Color development 38.5 ℃ 73 seconds 320ml 17L Bleach-fix 38 ℃ 74 seconds 88ml 17L Rinse 38 ℃ 33 seconds --- 7.5L Rinse 38 ℃ 33 seconds --- 7.5L Rinse 38 ℃ 41 seconds 385ml 7.9L Dry 60-80 ℃ 57 seconds * Replenishment amount is per 1m ² of light-sensitive material (rinse is 3 tank counter current method to →)

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Optical brightener (FL-1 below) 5.0g 7.5g Triisopropanolamine 8.8g 8.8g Sodium paratoluene sulfonate 10.0g 18.0g Sodium paratoluenesulfinate 5.0g 6.0g Ethylenediaminetetraacetic acid 4.0g 4.0g Sodium sulfite 0.10g 0.10g Potassium chloride 8.6g −   4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.50g 0.50g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 12.1g 14.8g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 4.8g 8.5g   Potassium carbonate 26.3g 26.3g   Add water 1000ml 1000ml   pH (25 ℃) 10.15 11.95

[0269]

[Chemical Formula 91]

[0270] Bleach-fix solution [tank solution] [replenisher]   800 ml of water 800 ml Ammonium thiosulfate (750g / l) 140ml 187ml m-Carboxybenzenesulfinic acid 20.4g 27.2g Ethylenediaminetetraacetic acid iron (III) ammonium 71.4g 95.4g Ethylenediaminetetraacetic acid 1.4g 1.4g Nitric acid (67%) 20.8g 41.7g Imidazole 14.6g 19.7g Ammonium sulfite 27.3g 36.4g Ammonium bromide 30.0 g 40.0 g   Add water to make 1000ml 1000ml pH (25 ° C) (adjusted with acetic acid / ammonia water) 6.13 5.5

[0271] Rinse solution [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less) 1000ml 1000ml   pH (25 ° C) 6.5 6.5

In the same manner, only yellow single color is developed.
Samples were also created in the same way. Printed pudding
The color reproducibility of the^*, A^*
And b ^*It was evaluated by. As a result, as shown in Table 1, the book
The invention sample 002 is superior in color reproducibility to the comparative sample 001.
It was found that there was little color mixing. Also, at the same time
In addition, a visual evaluation showed that the whiteness of the white background was also excellent.
I found out that

[0273]

[Table 1]

Exemplified compound (3) of the yellow dye-forming coupler of Sample 002 was prepared as exemplified compounds (23), (31),
(32), (33), (36), (37), (39),
Samples having equimolar amounts changed to (43) and (45) were prepared, and the same evaluation was performed. As a result, almost the same result as the sample 002 was obtained.

[0275]

According to the silver halide color light-sensitive material and the image forming method of the present invention, it is possible to form an image having high color reproducibility and stability and high productivity in an area modulation color proof. Further, the light-sensitive material of the present invention is mainly used for a color image forming method using a maximum color density and having a large amount of coated silver, and has excellent stability, high productivity, excellent color reproducibility, and cost reduction. be able to. Furthermore, in the image forming method using a negative tone type silver halide photographic light-sensitive material having a high contrast for forming a high-definition image of the present invention, gradation characteristics by a semiconductor laser or LED scanning exposure system are good (in a high contrast), In addition, color reproducibility can be improved.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyoshi Takeuchi             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H016 AB02 AB03 BE02 BF00

Claims (4)

[Claims] 1. A silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are provided on a support. A silver halide color light-sensitive material which has at least one layer and is exposed based on digital image data for area gradation, wherein the yellow dye-forming coupler has the following general formula (I):
A silver halide color light-sensitive material characterized by being a yellow dye-forming coupler represented by: [Chemical 1] In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X
Represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. 2. A silver halide emulsion layer containing a cyan dye forming coupler, a silver halide emulsion layer containing a magenta dye forming coupler, and a silver halide emulsion layer containing a yellow dye forming coupler on a support. A silver halide color light-sensitive material having at least one layer and forming an image by substantially using the maximum density of each light-sensitive layer without using the density of a gradation portion, wherein the yellow dye-forming coupler has the following structure. A silver halide color light-sensitive material which is a yellow dye-forming coupler represented by formula (I). [Chemical 2] In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X
Represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. 3. A silver halide emulsion layer containing a cyan dye forming coupler, a silver halide emulsion layer containing a magenta dye forming coupler, and a silver halide emulsion layer containing a yellow dye forming coupler on a support. A silver halide color light-sensitive material having at least one layer and capable of drawing a fine line having a line width of 30 μm or less, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I). A silver halide color light-sensitive material characterized by: [Chemical 3] In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X
Represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. 4. A silver halide emulsion layer containing a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler are provided on a support. An image forming method in which a silver halide color light-sensitive material having at least one layer each is exposed and then color developed, wherein the yellow dye-forming coupler is a yellow dye-forming coupler represented by the following general formula (I): An image formation characterized by exposing based on digital image data for area gradation or / and forming an image using substantially only the maximum density of each photosensitive layer without using the density of the gradation part Method. [Chemical 4] In the formula, Q represents a nonmetallic atom group forming a 5- to 7-membered ring together with -N = C-N (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 and may be bonded to each other to form a ring. X
Represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent.