JP2001022037A - Processing method for silver halide color photographic sensitive material, image forming method and manufacture of color proof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance dot reproducibility, to ensure stability even to a change of a processing solution and to enhance the fastness of an image, in particular the heat and moisture resistances and color reproducibility by disposing at least one black image information forming silver halide emulsion layer on a substrate and incorporating a specified compound. SOLUTION: The silver halide color photographic sensitive material has at least one black image information forming silver halide emulsion layer on the substrate and contains at least one compound of the formula, wherein Cp is the residue of a coupler, SOL is a solubilizing group, (n) is an integer of 1-3 and Ball is a diffusion resistant group which can be released in coupling reaction with the oxidized body of a color developing agent. The compound of the formula is preferably a compound which does not substantially contribute to image formation even when it couples with the oxidized body of the color developing agent. The residue of a dye forming coupler used in an ordinary silver halide photosensitive material may be used as the residue Cp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for producing a proof color image (color proof) from a plurality of black and white halftone images obtained by color separation and halftone image conversion in a color plate making and printing process. The present invention relates to a silver halide color photographic light-sensitive material (hereinafter, also referred to as "color light-sensitive material" or "photosensitive material"), a processing method thereof, an image forming method thereof, and a method of producing a color proof using the same.

[0002]

2. Description of the Related Art Conventionally, in a color plate making / printing process, a method for obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion is to use a photopolymer or a diazo compound. An overlay method for forming a color image and a surprint method are known.

The overlay method is very simple, has a low production cost, and has the advantage that it can be used for proofreading only by stacking film sheets of four colors (subtractive primary colors and black). The drawback is that gloss is produced by the overlapping, which results in a texture different from that of the printed matter.

In the surprint method, a colored image is superimposed on a single support. A method of obtaining a colored image by toner development utilizing the tackiness of a photopolymerizable material is disclosed in US Pat. No.582,327, No.3,6
No. 07,264 and 3,620,726.

Further, a color proof is obtained by transferring the image to a support using a photosensitive colored sheet, forming an image by exposure and development, laminating another colored sheet thereon, and repeating the same process. The method of making is JP 4
It is known from JP-A-7-27441 and JP-A-56-501217.

Further, a method of transferring each colored image obtained by exposing and developing a corresponding color separation film using a photosensitive colored sheet and forming the same on one support is disclosed in Japanese Unexamined Patent Publication No.
No. 9-97140. Since there is an advantage that a coloring material similar to the printing ink can be used as a toner for forming these images and a coloring agent for the coloring sheet, the color tone of the obtained color proof is close to that of a printed matter.

[0007] However, these methods have the drawback that images must be superimposed or transferred in the process of producing a color proof, which requires a long operation time and high production cost.

As a solution to such a disadvantage, a method for producing a color proof by using a silver halide color photographic light-sensitive material having a white support is disclosed in Japanese Patent Application Laid-Open No. 56-13313.
No. 9, No. 56-104335, No. 62-280746
No. 62-280747, No. 62-280748
Nos. 62-280747 and 62-280750
And No. 62-28049.

In this method, a plurality of color-separated black and white halftone images converted from a color original into color-separated halftone images are sequentially printed on one sheet of color paper by a method such as close-contact printing to perform color development. The color image formed by the dye formed from the coupler imagewise by color development and color development is used as a proofing image.

JP-A-1-260629, JP-A-61-2
JP-A No. 233732 and JP-A-4-1632 describe photosensitive materials having four emulsion layers of yellow, magenta, cyan, and black having different spectral sensitivities, and improved color reproducibility of a black image. For this reason, an image similar to a printed matter is obtained, and is used as a preferable technique. However, as the number of layers increases, the scattering of light increases, the reproducibility of halftone dots deteriorates, and particularly, the deterioration is remarkable in the layer closest to the support.

Further, it is apparent that the fastness, especially heat resistance, moisture resistance and color reproducibility of a cyan image obtained from a conventionally used phenolic cyan coupler are deteriorated when a black image forming layer is provided. It became.

On the other hand, a compound that does not contribute to the formation of a dye image is added to a direct positive silver halide color photographic light-sensitive material containing internal latent image type silver halide grains, so that the maximum image density is high and the minimum image density is low. A method for obtaining a good image is known from JP-A-6-258773. However, application to a silver halide color photographic light-sensitive material containing at least one layer containing a black image information-forming silver halide emulsion is disclosed. Not touched at all. The present inventors have conducted intensive studies. As a result, when the compound represented by the general formula (I) was applied to a photosensitive material containing a silver halide emulsion for forming black image information, the dot reproducibility was surprisingly deteriorated. Was greatly improved, and it was found that it was stable against fluctuations in the processing solution. In addition, it has been found that the robustness of a cyan image, particularly heat resistance and moisture resistance, is greatly improved, and that the color reproducibility of the cyan image is greatly improved.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an excellent halftone dot reproducibility and a stability with respect to fluctuations in a processing solution.
An object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in image fastness, especially heat resistance, humidity resistance and color reproducibility, a processing method thereof, an image forming method and a method of producing a color proof.

[0014]

The above object of the present invention has been attained by the following constitutions.

1. A silver halide color photographic light-sensitive material comprising at least one black image information forming silver halide emulsion layer on a support, and at least one compound represented by the following general formula (I). .

[0016]

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Wherein Cp represents a coupler residue,
L represents a solubilizing group; n represents an integer of 1 to 3;
11 represents a diffusion-resistant group which can be eliminated during the coupling reaction with the oxidized form of the color developing agent. ] 2. 2. The silver halide color photographic material as described in 1 above, which contains at least one kind of coupler represented by the following general formula (II).

[0018]

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[In the formula, R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, m represents an integer of 0 to 2,
Is 0, R ¹ represents an electron-withdrawing group, when m is 1 or 2, at least one of R ¹ and R ² represents an electron-withdrawing group, and when m is 2, a plurality of R ² Each 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 leaving upon coupling with an oxidized form of a color developing agent. Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the heterocyclic ring may be further bonded to a benzene ring or the like. ] 3. 3. The silver halide color photographic light-sensitive material as described in 1 or 2 above, comprising at least one silver halide emulsion layer containing internal latent image type silver halide grains.

4. 4. The silver halide according to any one of the above items 1 to 3, wherein the silver halide emulsion layer contains at least one silver halide emulsion layer containing internal latent image type silver halide grains nucleated by a nucleating agent. Color photographic light-sensitive material.

5. 5. A method for processing a silver halide color photographic light-sensitive material, comprising subjecting the silver halide color photographic light-sensitive material according to any one of the above items 1 to 4, to image exposure, to uniform exposure over the entire surface, and to perform fogging.

6. An image forming method comprising exposing the silver halide color photographic light-sensitive material described in any one of the above items 1 to 4 with a laser light source, developing, and forming an image.

7. 5. A method for producing a color proof, comprising forming a halftone dot image using the silver halide color photographic light-sensitive material described in any one of 1 to 4 above.

Hereinafter, the present invention will be described in detail.

Hereinafter, the compound represented by formula (I) in the present invention will be described in detail. General formula (I)
Is preferably a compound which does not substantially contribute to image formation even when coupled with an oxidized form of a color developing agent.

"Substantially does not contribute to image formation" means that even if it reacts with the oxidized form of the color developing agent and remains in the light-sensitive material after coupling, it has an absorption that affects the image in the visible light region. Or a compound that elutes into the processing solution after coupling and does not remain in the light-sensitive material.

In the present invention, Cp of the compound represented by the above general formula (I) is a coupler residue, and its structure is not particularly limited, and yellow, magenta, and cyan used in ordinary silver halide photosensitive materials are used. Can be used. When Cp represents a yellow coupler residue, for example, pivaloylacetoanilide type,
Benzoylacetanilide type, malon diester type, for example, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malonester monoamide type, benzoxazolylacetamide type, benzimidazolylacetamide type, quinazolin-4-one-2-yl Acetanilide-type or cycloalkanoylacetamide-type coupler residues are exemplified.

When Cp represents a magenta coupler residue,
For example, 5-pyrazolone type, pyrazolo [1,5-a] benzimidazole type, pyrazolo [1,5-b] [1,2,
4] Triazole type, pyrazolo [5,1-c] [1,
2,4] triazole type, imidazo [1,2-b] pyrazole type, pyrrolo [1,2-b] [1,2,4] triazole type, pyrazolo [1,5-b] pyrazole type or cyanoacetophenone type Coupler residue.

When Cp represents a cyan coupler residue, for example, phenol type, naphthol type, pyrrolo [1,2-
b] [1,2,4] triazole type, pyrrolo [2,1-
c] [1,2,4] triazole-type or 2,4-diphenylimidazole-type coupler residues.

Examples of the compound residue which does not substantially produce a colored compound even when reacted with an oxidized developing agent include coupler residues such as indanone type and acetophenone type.

A preferred example of Cp is represented by the following general formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), (Cp-9), (Cp-10), (Cp-11)
Or a coupler residue represented by (Cp-12), and the coupler of the present invention having such a coupler residue has a high coupling speed and is preferred.

[0032]

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[0033]

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[0034]

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In the above formula, the free bond derived from the coupling position represents the bonding position of the group represented by Ball. In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ ,
R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , R
Each of ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ preferably has 10 or less carbon atoms. The coupler residue represented by Cp is bonded to at least one solubilizing group represented by SOL. That is, at least one of R ₅₁ or R _{52 in} the general formula (Cp-1), and at least one of R ₅₁ , R ₅₂ or R _{53 in} the general formula (Cp-2) corresponds to the general formula (Cp
In p-3), at least one of R ₅₄ or R ₅₅ , and in formulas (Cp-4) and (Cp-5), at least one of R ₅₆ or R ₅₇ is the same as in general formula (Cp-
In 6), at least one of R ₅₈ or R ₅₉ , in the general formula (Cp-7), at least one of R ₅₉ or R ₆₀ , and in the general formula (Cp-8), R ₆₁ or R _61
62 has at least one of the general formulas (Cp-9) and (Cp-9)
In p-10), at least one R ₆₃ represents R ₆₄ in general formulas (Cp-11) and (Cp-12),
At least one of R _{65 and} R _{66 has} a solubilizing group represented by SOL as a substituent.

The solubilizing group represented by SOL imparts diffusibility to a dye formed by the coupling reaction of the compound of the present invention with an oxidized form of a color developing agent, so that the compound can be dispersed during photographic processing. Groups which give characteristics that can be released from the silver halide photographic light-sensitive material in an alkaline environment, such as an ionizable hydroxyl group, a carboxyl group and a sulfo group, and a group composed of a salt thereof (eg, a hydroxyl group, a carboxyl group) And a hydrogen atom of a sulfo group substituted by an alkali metal such as Na or K, an alkaline earth metal such as Ca or Mg, or an ammonium ion. Further, those containing a group composed of these ionizable groups and salts thereof, for example, one or two of the groups composed of these groups or salts thereof
One or more of them may be a group which is bonded to Cp via an alkyl group having 16 or less carbon atoms, an aryl group or a heterocyclic group. These alkyl group, aryl group or heterocyclic group having 16 or less carbon atoms may be bonded to a crosslinking group for bonding these groups to Cp. Representative crosslinking groups include -O-, -S-, -CO-, -COO-,
-OCO-, -NH-, -CONH-, -NHCO-,
_{-NHCONH -, - SO 2 NH -} , - NHSO 2 - and the like. The alkyl group, aryl group and heterocyclic ring having 16 or less carbon atoms include, for example, a halogen atom, an amino group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, an alkyl group, an alkoxy group, and an aryl group. It may have one or two or more substituents.

The solubilizing group represented by SOL of the general formula (I) includes (1) a hydroxyl group, a carboxyl group, a sulfo group directly bonded to a non-coupling position of Cp, and an ionizable salt thereof. (2) the number of carbon atoms having a group attached to a non-coupling position of Cp and having one or more hydroxyl groups, carboxy groups, sulfo groups or ionizable salts thereof Up to 16 alkyl, aryl and heterocyclic groups,
And a group in which the alkyl group, the aryl group, or the heterocyclic group is bonded to a non-coupling position of Cp via a crosslinking group such as an amide group or a carbonyl group.

Hereinafter, R _{51 to} R ₆₆ , a, b, d and e will be described in detail. In the following, R ₄₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅
Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₅₁ has the same meaning as R ₄₁ . a is 0 or 1
Represents R ₅₂ and R ₅₃ each have the same meaning as R ₄₃ .
When R ₅₂ is not hydrogen atom in the general formula (Cp-2), may form a ring of 5-7 members by bonding R ₅₂ and R _51. b represents 0 or 1. R ₅₄ represents a group having the same meaning as _{R 41, R 41 CON (R} 43) - _{group, R 41 SO 2 N (R} 43) -
A R ₄₁ N (R ₄₃ ) — group, an R ₄₁ S— group, an R ₄₃ O— group, or an R ₄₅ N (R ₄₃ ) CON (R ₄₄ ) — group. R ₅₅ is R
Represents a group having the same meaning as ₄₁ . R ₅₆ and R ₅₇ each have the same meaning as the R ₄₃ group, R ₄₁ S— group, R ₄₃ O— group, R ₄₁ CON
(R ₄₃ ) —, R ₄₁ OCON (R ₄₃ ) — or R ₄₁ S
Represents an O ₂ N (R ₄₃ ) — group. R ₅₈ represents a group having the same meaning as R ₄₃ . R ₅₉ is a group of the same meaning as R _41, R ₄₁ CON
(R ₄₃ ) —, R ₄₁ OCON (R ₄₃ ) —, R ₄₁ SO ₂
An N (R ₄₃ )-group, an R ₄₃ N (R ₄₄ ) CON (R ₄₅ )-group,
R ₄₁ O— group, R ₄₁ S— group, halogen atom or R ₄₁ N
(R ₄₃ )-represents a group. d represents 0 to 3. When d is plural, plural R _59s represent the same substituent or different substituents. R ₆₀ represents a group having the same meaning as R ₄₃ . R ₆₁ is R ₄₃
R ₄₃ OSO ₂ —, R ₄₃ N (R ₄₄ ) S
O ₂ group, R ₄₃ OCO— group, R ₄₃ N (R ₄₄ ) CO— group, cyano group, R ₄₁ SO ₂ N (R ₄₃ ) CO— group, R ₄₃ CON
(R ₄₄₎ CO- _{group, R 43 N (R 44)} SO 2 N (R 45) C
O- group, R ₄₃ N (R ₄₄ ) CON (R ₄₅ ) CO- group, R _{43
N (R 44) SO 2 N} (R 45) SO 2 - group, R ₄₃ N (R ₄₄₎
CON (R ₄₅ ) represents a SO ₂ — group. R ₆₂ is a group of the same meaning as R _41, R ₄₁ CONH- group, R ₄₁ OCONH- group, R ₄₁
SO ₂ NH— group, R ₄₃ N (R ₄₄ ) CONH— group, R ₄₃ N
(R ₄₄ ) represents a SO ₂ NH— group, an R ₄₃ O— group, an R ₄₁ S— group, a halogen atom or an R ₄₁ NH— group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON (R ₄₄ ) —, R ₄₃ N (R ₄₄ )
CO— group, R ₄₁ SO ₂ N (R ₄₃ ) — group, R ₄₁ N (R ₄₃ )
SO ₂ — group, R ₄₁ SO ₂ — group, R ₄₃ OCO— group, R ₄₃ OS
An O ₂ — group, a halogen atom, a nitro group, a cyano group or R
₄₃ represents a CO-group. e is an integer of 0 to 4, f is 0
Represents an integer of 1 to 3. Each represent the same or different when there are a plurality of R ₆₂ or R _63. R ₆₄ , R
₆₅ and R ₆₆ each have the same meaning as the R ₄₃ group, and R ₄₁ S-
Group, R _{43 O-group, R 41 CON (R 43)} - group, R ₄₁ SO ₂
An N (R ₄₃ ) — group, an R ₄₁ OCO— group, an R ₄₁ OSO ₂ — group,
R ₄₁ SO ₂ — group, R ₄₁ N (R ₄₃ ) CO— group, R ₄₁ N (R
₄₃ ) represents an SO ₂ — group, a nitro group or a cyano group.

In the above description, the alkyl group is one having 1 to 1 carbon atoms.
0, preferably 1 to 6, saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Representative examples include methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-
Examples include ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, and n-decyl. In the above, the aryl group is an aryl group having 6 to 10 carbon atoms, preferably a substituted or unsubstituted phenyl or a substituted or unsubstituted naphthyl. In the above description, the heterocyclic group has 1 to 10, preferably 1 to 6, constituent atoms, and is selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and is preferably a substituted or unsubstituted 3- to 8-membered ring. Is a heterocyclic group. Representative examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl,
1,3,4-thiadiazol-2-yl, 1,2,4-
Examples include a triazol-2-yl group or 1-indolinyl.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents include a halogen atom, R ₄₇ O—, R ₄₆ S—, and R ₄₇ CON.
(R ₄₈ ) —, R ₄₇ N (R ₄₈ ) CO—, R ₄₆ OCON
(R ₄₇ ) —, R ₄₆ SO ₂ N (R ₄₇ ), R ₄₇ N
(R ₄₈ ) SO ₂ — groups, R ₄₆ SO ₂ — groups, R ₄₇ OCO— groups,
An R ₄₇ NCON (R ₄₈ ) — group, an R ₄₇ CONHSO ₂ — group,
R ₄₇ NHCONHSO ₂ — group, a group having the same meaning as R ₄₆ ,
₄₇ N (R ₄₈₎ - group, R ₄₆ CO ₂ - group, R ₄₇ OSO ₂ - group,
Examples include a cyano group or a nitro group. Here, R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group,
R ₄₇ and R ₄₈ each represent an alkyl group, an aryl group, a hetero group, or a hydrogen atom. The meaning of the alkyl group, the aryl group or the heterocyclic group is the same as defined above.

Next, preferred ranges of R _{51 to} R ₆₆ , a, b, d and e will be described. When a is 0, R ₅₁ is preferably an alkyl group, an aryl group or a heterocyclic group, and when a is 1, an alkyl group or an aryl group is preferable. R
₅₂ and R ₅₅ are preferably an aryl group. R ₅₃ is preferably an aryl group when b is 1 and a heterocyclic group when b is 0. R
₅₄ is preferably an R ₄₁ CONH— group or an R ₄₁ N (R ₄₃ ) — group. R ₅₆ and R ₅₇ are preferably an alkyl group, an R ₄₁ O-group, or an R ₄₁ S-group. R ₅₈ is preferably an alkyl group or an aryl group. In the general formula (Cp-6), R ₅₉ is a chlor atom, an alkyl group or R ₄₁ CON (R ₄₃ )-
Groups are preferred. d is preferably 1 or 2. R ₅₈ is preferably an aryl group. In the general formula (Cp-7), R ₅₉ is preferably an R ₄₁ CON (R ₄₃ )-group. General formula (Cp-
In 7), d is preferably 1. R ₆₁ R ₄₃ OSO ₂ −
R ₄₃ N (R ₄₄ ) SO ₂ , R ₄₃ OCO—, R ₄₃ N
(R ₄₄₎ CO- group, a cyano _{group, R 41 SO 2 N (R} 43) C
O-group, R ₄₃ CON (R ₄₄ ) CO-group, R ₄₃ N (R ₄₄ )
SO ₂ N (R ₄₅ ) CO— group, R ₄₃ N (R ₄₄ ) CON (R
₄₅ ) CO- groups are preferred. In the general formula (Cp-8), e is preferably 0 or 1. R ₆₁ is R ₄₁ OCON
(R ₄₃ ) —, R ₄₁ CON (R ₄₃ ) — or R ₄₁ SO
_{A 2} N (R ₄₃ )-group is preferred, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is an R ₄₁ CON (R ₄₃ ) — group, R ₄₁ SO ₂ N
(R ₄₃ ) —, R ₄₁ N (R ₄₃ ) SO ₂ —, R ₄₁ SO ₂ —
Groups, R ₄₁ N (R ₄₃ ) CO—, nitro or cyano. In the general formula (Cp-10), R ₆₃ is R ₄₃
N (R ₄₄ ) CO—, R ₄₃ OCO—, or R ₄₃ CO—
Groups are preferred. General formulas (Cp-11) and (Cp-1)
In 2), R ₆₄ and R ₆₅ are R ₄₁ OCO— groups, R ₄₁
OSO ₂ — group, R ₄₁ SO ₂ — group, R ₄₄ N (R ₄₃ ) CO—
Groups, R ₄₄ N (R ₄₃ ) SO ₂ — groups or cyano groups are preferred, and R ₄₁ OCO— groups, R ₄₄ N (R ₄₃ ) CO— groups or cyano groups are particularly preferred. R ₆₆ is preferably a group having the same meaning as R ₄₁ . Each of R _{51 to} R ₆₆ preferably has a total carbon number of 18 or less including a substituent, and more preferably 1 to _66.
0 or less.

Next, the group represented by Ball will be described. The group represented by Ball represents a non-diffusible group having a total carbon number of 10 to 40 bonded to the coupling position of the group represented by Cp via an oxygen atom, a sulfur atom or a nitrogen atom. B
Preferred examples of the group represented by all include R ₈₁ O-
Group, R ₈₁ CO ₂ — group, R ₈₁ OCO ₂ — group, R ₈₁ N (R ₈₂ )
CO ₂ -group, R ₈₁ SO ₂ O-group, R ₈₁ S-group, R ₈₁ COS
Group, R ₈₁ SO ₂ S— group, R ₈₁ N (R ₈₂ ) — group, R ₈₁ C
Represents an ON (R ₈₂ ) — group or a saturated or unsaturated heterocyclic group bonded through a nitrogen atom.

R ₈₁ represents a non-diffusible substituent. Preferably, R ₈₁ is an aliphatic group (a linear, branched or cyclic alkyl group having 10 to 40 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, for example, decyl, dodecyl, hexadecyl, octadecyl, 3- ( 3-pentadecylphenoxy) propyl, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamido} phenyl} propyl, 2-ethoxytridecyl,
Trifluoromethyl, cyclopentyl, 3- (2,4-
Di-t-amylphenoxy) propyl, 3-dodecyloxypropyl, 2- (1-carboxytridecylthio)
Ethyl), an aryl group (an aryl group having 10 to 40 carbon atoms, for example, 4-t-butylphenyl, 2,4-di-t
-Amylphenyl, 4- (4- (2,4-di-t-amylphenoxy) butanamido) phenyl, 1-naphthyl), a heterocyclic group (a heterocyclic group having 10 to 40 carbon atoms, for example, 5-decyl- 2-furyl). R ₈₂ represents a group having the same meaning as R ₈₁ or a hydrogen atom. R ₈₁ and R ₈₂ may further have a substituent, and preferred substituents are the same as those described above as typical substituents when the alkyl group, the aryl group, and the heterocyclic group have a substituent. But,
The carbon number of those substituents may be 10 or more.

When Ball represents a saturated or unsaturated hetero group bonded by a nitrogen atom, Ball is preferably represented by the following formulas (B-1), (B-2), (B-3) and (B-3).
-4) or (B-5).

[0045]

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In the general formula (B-1), Z ₁ represents a nonmetallic atomic group necessary for forming a 5-membered ring together with one nitrogen atom and two carbonyl carbon atoms. In the general formulas (B-2) and (B-3), X ₁ and Y each represent a nitrogen atom or —C (R ₁₁ ) =, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ represents a substituent And n
1 represents an integer of 0 to 4, and when n1 is 2 or more, a plurality of R
₁₂ may be the same or different. In formula (B-4) and (B-5), represents V, W and T a are each a nitrogen atom or _{-C (R 13) =, R} 13 and R ₁₄ represents a hydrogen atom or a substituent.

The formulas (B-1), (B-2) and (B-
The groups represented by 3), (B-4) and (B-5) will be described in detail below. In the general formula (B-1),
Z ₁ represents a nonmetallic atomic group necessary for forming a 5-membered ring together with one nitrogen atom and two carbonyl carbon atoms, and has a diffusion-resistant group having 8 or more carbon atoms. General formula (B
Preferred examples of the basic skeleton of the group represented by -1) include 2,4-dioxo-1,3-imidazolidin-3-yl and 2,4-dioxo-1,3-oxazolidin-3-
Yl, 3,5-dioxo-1,2,4-triazolidine-4-yl, succinimide, phthalimide and the like. Examples of the diffusion-resistant group having 8 or more carbon atoms contained in Z ₁ include R ₉₆ , R ₉₆ O—, R ₉₇ CO—, and R ₉₆ OCO ₂ —.
Group, R ₉₆ N (R ₉₇ ) CO ₂ — group, R ₉₆ N (R ₉₇ ) SO ₂ O
Group, R ₉₆ SO ₂ O— group, R ₉₇ CO— group, R ₉₆ OCO—
R ₉₇ N (R ₉₈ ) CO—, R ₉₆ N (R ₉₇ ) —, R
₉₆ CON (R ₉₇ ) -group, R ₉₆ OCON (R ₉₇ ) -group, R
₉₆ N (R ₉₇ ) CON (R ₉₈ ) — group, R ₉₆ SO ₂ N
An (R ₉₇ )-group, an R ₉₆ N (R ₉₇ ) SO ₂ N (R ₉₈ )-group,
R ₉₆ S— group, R ₉₆ SO—O— group, R ₉₆ SO ₂ — group, R ₉₆
And N (R ₉₇ ) SO ₂ — groups. Where R ₉₆ is R
Represent the same meanings of the group with _81, R ₉₇ and R ₉₈ represents a group having the same meaning as a hydrogen atom or R _81.

In the general formulas (B-2) and (B-3), X ₁ and Y are each a nitrogen atom or -C
(R ₁₁ ) =, R ₁₁ represents a hydrogen atom or a substituent, R ₁₂ represents a substituent, n1 represents an integer of 0 to 4,
n1 plurality of R ₁₂ when two or more may be the same or different. Preferred examples of the basic skeleton of the group represented by formula (B-2) or (B-3) include benzotriazol-1-yl, benzotriazol-2-yl, benzimidazol-1-yl, indolyl and the like. No.
Preferred examples of the substituent represented by R ₁₁ and R ₁₂ are the same as those mentioned above as typical substituents when the alkyl group, the aryl group and the heterocyclic group have a substituent. At least one of R ₁₁ and 0 to 4 R ₁₂ represents a non-diffusible group having 8 or more carbon atoms, and a preferable non-diffusible group is included in Z ₁ of the general formula (B-1). It is the same as the one cited as the diffusion-resistant group having 8 or more carbon atoms.

In the general formulas (B-4) and (B-5), V, W and T each represent a nitrogen atom or -C (R
₁₃ ) =, and R ₁₃ and R ₁₄ represent a hydrogen atom or a substituent. However, V, W and T are not nitrogen atoms at the same time.

Preferred examples of the basic skeleton of the group represented by formula (B-4) or (B-5) include 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazole-1
-Yl, 1,2,4-triazol-4-yl, 1,
Examples thereof include 2,3-triazol-1-yl, 1,2,3-triazol-2-yl, and pyrrolyl. Preferred examples of the substituent represented by R ₁₃ and R ₁₄ are the same as those described above as typical substituents when the alkyl group, the aryl group, and the heterocyclic group have a substituent.
At least one of R ₁₄ and 0 to 3 R ₁₃ represents a non-diffusible group having 8 or more carbon atoms, and a preferable non-diffusible group is included in Z ₁ of the general formula (B-1). It is the same as the one cited as the diffusion-resistant group having 8 or more carbon atoms.

Specific representative examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

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The amount of the compound of the present invention represented by the general formula (I) in the silver halide color photographic light-sensitive material may be any amount as long as the effects of the present invention can be obtained. Is preferably 0.1 mol% to 50 mol%,
More preferably, it is 0.5 mol% to 20 mol%.

The compound represented by the general formula (I) used in the present invention may contain at least one compound in a light-sensitive material.
It may be contained in the black image forming layer as long as it is contained in the layer. However, the effect is great when it is contained in the cyan image-forming layer and the yellow image-forming layer, and the effect is particularly great when it is contained in the yellow image-forming layer. Next, the coupler represented by formula (II) contained in the cyan image forming layer used in the light-sensitive material of the present invention will be described in detail.

The electron-withdrawing group represented by R ¹ or R ² in the general formula (II) is preferably a substituent having a substituent constant σp defined by Hammett of +0.20 or more. Specifically, sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogenated alkoxy,
Examples thereof include halogenated aryloxy, pyrrolyl, tetrazolyl, and other groups, and halogen atoms.

Examples of the sulfonyl group include groups such as alkylsulfonyl, arylsulfonyl, and halogenated alkylsulfonyl and arylsulfonyl halides; examples of the sulfinyl group include groups such as alkylsulfinyl and arylsulfonyl; Groups such as sulfonyloxy and arylsulfonyloxy; examples of the sulfamoyl group include N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl,
A group such as -alkyl-N-arylsulfamoyl; a phosphoryl group as a group such as alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, or arylphosphoryl; a carbamoyl group as N, N-dialkylcarbamoyl, N, N- Diarylcarbamoyl,
Groups such as N-alkyl-N-arylcarbamoyl; examples of the acyl group include groups such as alkylcarbonyl and arylcarbonyl;

The acyloxy group is preferably an alkylcarbonyloxy group.

Examples of the oxycarbonyl group include groups such as alkoxycarbonyl and aryloxycarbonyl.

The halogenated alkoxy group is preferably an α-halogenated alkoxy group, and the halogenated aryloxy group is preferably a group such as tetrafluoroaryloxy and pentafluoroaryloxy.

The pyrrolyl group includes a group such as 1-pyrrolyl, and the tetrazolyl group includes a group such as 1-tetrazolyl.

In addition to the above substituents, trifluoromethyl,
Heptafluoro-i-propyl, nonylfluoro-t-
Groups such as butyl, a tetrafluoroaryl group, a pentafluoroaryl group, and the like are also preferably used.

As the substituent other than the electron-withdrawing group represented by R ¹ or R ² , there can be mentioned various substituents, and there is no particular limitation. Representative examples thereof include alkyl, aryl, anilino, and acylamino. , Sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl,
Cycloalkenyl, alkynyl, heterocycle, alkoxy,
Each of aryloxy, heterocyclic oxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto Groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As the aryl group, a phenyl group is preferable.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. The alkyl component and the aryl component of the alkylthio group and the arylthio group are as described above. Examples include an alkyl group and an aryl group.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 12 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched. A cycloalkenyl group having 3 to 12 carbon atoms;
Particularly, those having 5 to 7 are preferable.

Examples of the ureido group include an alkylureido group and an arylureido group; examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; And the like. Specifically, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl and the like; as the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable. , 6-tetrahydropyranyl-2-oxy, 1-phenyltetrazol-5-oxy, etc .; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio, 2-benzothiazolylthio , 2,4-diphenoxy-1,3,5-triazole-6-thio and the like; as siloxy groups, trimethylsiloxy, triethylsilo Shi, dimethylbutyl siloxy like. Examples of the imide group, succinimide, 3-heptadecyl succinic acid imide, phthalimide, glutarimide and the like; the spiro compound residue, spiro [3.3] heptane -
1-yl and the like: As bridged hydrocarbon compound residues, bicyclo [2.2.1] heptane-1-yl, tricyclo [3.1.13.7] decan-1-yl, 7,7-dimethyl -Bicyclo [2.2.1] heptane-1-yl and the like.

In the general formula (II), examples of the group capable of leaving upon coupling with the oxidized form of the color developing agent represented by X include, for example, a halogen atom, alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy , Alkoxycarbonyl, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, N Examples include groups such as a nitrogen-containing heterocyclic ring bonded by an atom. X is preferably a hydrogen atom, a halogen atom, an alkoxy, an aryloxy, an arylthio, or a nitrogen-containing heterocyclic group linked by an N atom, and particularly preferably a hydrogen atom or a halogen atom. In the general formula (II), examples of the nitrogen-containing heterocyclic ring Z which may be condensed with a benzene ring or the like include, for example, heterocyclic rings such as pyrazole, imidazole, benzimidazole, triazole, tetrazole, pyrimidine, pyrazine and pyridazine. And
Further, each of these rings may have a substituent.

Specific examples of the coupler represented by formula (II) are shown below, but the invention is not limited thereto.

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The coupler of the present invention is usually used in the contained silver halide emulsion layer in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ³ mol per mol of silver halide.
It can be used in the range of ^-1 mol.

When the present invention is used in combination with these cyan couplers, the cyan image is excellent in fastness, particularly heat resistance, humidity resistance and color reproducibility, and is preferable.

An oil-in-water droplet is used for adding a compound which does not substantially contribute to image formation or other organic compounds even when coupled with an oxidized product of a coupler or a color developing agent used in the color light-sensitive material of the present invention. When the emulsion-dispersion method is used, it is usually dissolved in a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary, in combination with a low-boiling and / or water-soluble organic solvent. Emulsifying and dispersing in a hydrophilic binder using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added.

As the high boiling point organic solvent, phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, phosphoric acid esters such as tricresyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferable. Used. or,
The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Particularly preferred compounds as the high boiling organic solvent are the compounds represented by the general formulas [HBS-I] and [HBS-II] described in JP-A-6-95283, page 22, and particularly preferred is [HBS-II]. -II].
Specific compounds include, for example, JP-A-2-124568.
Nos. 1-1 to II-95 described on pages 53-68.
Can be mentioned.

In the color light-sensitive material of the present invention, at least one yellow image forming silver halide emulsion layer (Y
An emulsion layer), at least one magenta image forming silver halide emulsion layer (referred to as M emulsion layer), at least one cyan image forming silver halide emulsion layer (referred to as C emulsion layer), and It has at least one black image forming silver halide emulsion layer (referred to as S emulsion layer).

Here, the S emulsion layer may be any emulsion layer capable of forming a black image by image exposure and development. As a preferred example, the S emulsion can be used in combination with a black image layer containing a black coupler. As another preferred example, the S emulsion can be used in combination with a black image layer containing a yellow coupler, a magenta coupler and a cyan coupler. It is also a preferable example that the S emulsion contributes to image formation of a plurality of layers and a black image is formed by combining a plurality of images by developing the S emulsion.
As an example of forming a black image by combining a plurality of images, for example, an S emulsion is contained in a yellow image layer for forming a yellow image, and a blue image (for example, a magenta image and a cyan image) which is a complementary color of the yellow image is separately provided. A blue image is formed by simultaneous formation.
There is an emulsion which contains an emulsion and forms a black image when the S emulsion is developed. Further, the S emulsion may be contained in the magenta image forming layer and its complementary color image forming layer, or the S emulsion may be contained in the cyan image forming layer and its complementary color image forming layer.

In another preferred example, the S emulsion is contained in any of the yellow image forming layer, the magenta image forming layer and the cyan image forming layer, and the S emulsion is developed to form a black image. In this case, the yellow image forming layer, the magenta image forming layer, and the cyan image forming layer may contain the Y emulsion, the M emulsion, and the C emulsion of the present invention, respectively. You may.

One of the most preferred embodiments of the present invention is
The Y emulsion layer, the M emulsion layer, and the C emulsion layer in the present invention each contain an S emulsion.

In another most preferred embodiment of the present invention, the S emulsion is contained in a black image-forming silver halide emulsion layer.

Further, one of the most preferred embodiments of the present invention is directed to a red image (for example, a magenta image) in which the S emulsion is a complementary color of the cyan image-forming silver halide emulsion layer (C emulsion layer) and the cyan image. And a yellow image is formed at the same time to form a red image.) Some of the forming layers also contain an S emulsion, and a black image is formed by developing the S emulsion.

The yellow image-forming silver halide emulsion layer (Y emulsion layer), the magenta image-forming silver halide emulsion layer (M emulsion layer), and the cyan image-forming silver halide emulsion layer (C emulsion layer) of the present invention. May be composed of a single layer or a plurality of layers. The order of application from the support can be arbitrarily selected.

The maximum photosensitive wavelength of each emulsion is from 350 to 900.
It can be arbitrarily selected between nm. One preferred embodiment is that the yellow image forming emulsion (Y emulsion) is in the blue region, the magenta image forming emulsion (M emulsion) is in the green region, the cyan forming emulsion (C emulsion) is in the red region, and the S emulsion is infrared. Area.
Also, in another preferred embodiment, the Y emulsion is 400 ±
30 nm, M emulsion 460 ± 30 nm, C emulsion 540
It is also preferable that the emulsions are set so that the emulsion wavelength is ± 30 nm and the S emulsion is 640 ± 30 nm, and the difference between the maximum photosensitive wavelengths of each emulsion is 20 nm or more. In yet another preferred example, the M emulsion is 5
80 nm, C emulsion 660 nm, Y emulsion 750 nm,
The S emulsion can be set to 850 nm. In still another preferred example, the Y emulsion is 540 nm and the M emulsion is 380 nm.
The m and C emulsions can be set to 460 nm, and the S emulsion can be set to 630 nm. These are only examples and are not limiting.

These Y emulsion, M emulsion, C emulsion and S emulsion can be realized by selecting from conventionally known spectral sensitizing dyes and performing sensitization.

The most preferred embodiment of the light-sensitive material of the present invention is, in order from the support, an antihalation layer, an intermediate layer, an infrared-sensitive emulsion layer containing a Y coupler, an intermediate layer, and a red light-sensitive layer containing a C coupler. Emulsion + green light-sensitive emulsion layer, intermediate layer, green light-sensitive emulsion layer containing red coupler, intermediate layer, blue light-sensitive emulsion layer containing M coupler, and a light-sensitive material in which a protective layer is coated on the uppermost layer. The compound represented by the general formula (I) according to the present invention may be added to any of the layers, but the red-sensitive emulsion containing a C coupler +
Most preferably, it is added to the green photosensitive emulsion layer. Here, the yellow image formation is controlled by the infrared-sensitive emulsion (Y emulsion) layer, the cyan image formation is controlled by the red-sensitive emulsion (C emulsion) layer, and the magenta image formation is controlled by the blue-sensitive emulsion (M emulsion) layer. A green photosensitive emulsion was used as the S emulsion described above, and this was used for the cyan image forming layer and the red image forming layer as described above. Is formed.

The light-sensitive material of the present invention is preferably a positive-type light-sensitive material. This positive type photosensitive material includes a direct positive type and a color reversal type photosensitive material, and a so-called positive image is formed by bleaching a dye at the same time as bleaching image-generated silver. A photosensitive material using a silver dye bleaching method, a photosensitive material using a color diffusion transfer method, and the like are included.

As the silver halide emulsion which can be used in the light-sensitive material of the present invention, an emulsion containing internal latent image type silver halide grains is particularly preferable, and an internal latent image type halide in which the grain surface is not previously fogged is used. Using a silver emulsion, after image exposure, fog processing (nucleation processing) is performed, and then surface development is performed, or after image exposure, a positive image can be directly obtained by performing surface development while performing fog processing. Those are also preferred. The emulsion containing the internal latent image type silver halide grains is defined as silver halide grains having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. Containing emulsion.

The internal latent image type silver halide emulsion which can be preferably used in the light-sensitive material of the present invention is any silver halide, for example, silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, iodoodor. Silver halide, silver chloroiodobromide and the like.

The fogging treatment may be performed by exposing the entire surface, may be performed chemically using a nucleating agent, or
A strong developing solution may be used, and heat treatment or the like may be used. However, it is preferable that the fogging treatment be performed by giving a full-surface exposure or chemically using a nucleating agent.

The nucleating agent is a substance which acts on the surface development processing of an internal latent image type silver halide emulsion which has not been previously fogged to directly form a positive image.

When the nucleating agent is contained in the photosensitive material,
It is preferably added to the internal latent image type silver halide emulsion layer, but as long as it diffuses during coating or processing and the nucleating agent is adsorbed on the silver halide, other layers such as an intermediate layer, an undercoat layer and It may be added to the back layer. When a nucleating agent is added to the processing solution, a developer or JP-A-58-178350 may be used.
It may be contained in a low pH pre-bath as described in the above item. Further, two or more nucleating agents may be used in combination.

Examples of the nucleating agent that can be used in the present invention include, for example, “Research Disclosure”, N.
o. 22534 (January 1983), pp. 50-54; 15162 (November 1976) 76-77
Page, the magazine, No. 23510 (November 1983) 34
Examples thereof include quaternary heterocyclic compounds and hydrazine compounds described on pages 6 to 352.

Examples of the quaternary heterocyclic nucleating agent include, for example, US Pat. Nos. 3,615,615 and 3,719,494;
Nos. 3,734,738, 3,759,901, 3,854,956, 4,094,683, 4,306,016, British Patent 1,283,835
No., JP-B-49-38164, and 52-19452
No. 52-47326, JP-A-52-69613
No. 52-3426, No. 55-138742, No. 60-11837 and the aforementioned "Research Disclosure" magazine No. 22534; 23213
(Pp. 267-270, issued August 1983). Further, as highly active quaternary salt compounds, JP-A Nos. 63-121042 and 63-301942,
JP-A-1-191132, JP-A-2-101450, JP-A-2-79038, and JP-A-2-101451 can be used. Particularly, a quaternary heterocyclic nucleating agent represented by the following general formula (N) is preferable.

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In the formula, Z ₂ represents a group of nonmetal atoms necessary for forming a 5- or 6-membered heterocyclic ring, and Z ₂ may be substituted with a substituent. R ₃ is an aliphatic group, and R ₄ is a hydrogen atom, an aliphatic group or an aromatic group. R ₃ and R ₄ may be substituted with a substituent. R ₄ may further form a ring by bonding with the heterocyclic ring completed by Z ₂ . However,
At least one of the groups represented by R ₃ , R ₄ and Z ₂ contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or forms a 6-membered ring with R ₃ and R ₄ , Form a dihydropyridinium skeleton.

Further, at least one of the substituents of R ₃ , R ₄ and Z ₂ may have a group for promoting adsorption to silver halide. Y ₁ is a counter ion for charge balance,
p is 0 or 1. Heterocycles completed with Z ₂ include, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium. Examples of the substituent of Z ₂ include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an acyloxy group, and an acylamino group. , A sulfonyl group, a sulfonyloxy group, a sulfonylamino group, a carboxyl group, an acyl group,
Examples include a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, a ureido group, a urethane group, a carbonate group, a hydrazine group, a hydrazone group, and an imino group.

The substituent of Z ₂ may be via an appropriate linking group. The aliphatic groups of R ₃ and R ₄ preferably have 1 to 1 carbon atoms.
Eight unsubstituted alkyl groups and substituted alkyl groups having 1 to 18 carbon atoms in the alkyl portion. The aromatic group represented by R ₄ preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Examples of the group which the substituents of R ₃ , R ₄ and Z ₂ may have to promote adsorption to silver halide include a thioamide group, a mercapto group and a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide group is preferably an acyclic thioamide group (for example, a thiourethane group, a thioureido group, etc.).

As the mercapto group, a heterocyclic mercapto group (for example, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,
3,4-oxadiazole, etc.) are preferred. The 5- or 6-membered nitrogen-containing heterocyclic ring comprises a combination of nitrogen, oxygen, sulfur and carbon, and preferably forms imino silver, and includes, for example, benzotriazole and aminothiatriazole.

When a nucleating agent is used, it is preferable to use a nucleating agent for promoting the action of the nucleating agent. A nucleation accelerator has substantially no function as a nucleating agent,
It refers to a substance that promotes the action of a nucleating agent to increase the maximum density of a direct positive image and / or accelerates the development time required to obtain a constant direct positive image density.

Examples of such a nucleation accelerator include tetrazaindenes, triazaindenes and pentaazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. And the compounds described in JP-A-63-106656, pp. 5-16. Also, JP-A-63
-226652, 63-106656, 63-
No. 8740.

The overall exposure, which is another preferred fogging treatment, is carried out by immersing or moistening the image-exposed photosensitive material in a developing solution or other aqueous solution and then uniformly exposing the entire photosensitive material. As the light source used here, any light source may be used as long as it has light in the photosensitive wavelength range of the photosensitive material.Also, high-intensity light such as flash light can be applied for a short time, and weak light can be applied. May be applied for a long time. Further, the time of the entire surface exposure can be varied over a wide range depending on the photographic light-sensitive material, development processing conditions, type of light source used, and the like so that the best positive image is finally obtained. In addition, it is most preferable that the exposure amount for the entire surface exposure be given in a certain fixed range in combination with the photosensitive material. Usually, when the exposure amount is excessively increased, the minimum density increases or desensitization occurs, and the image quality tends to be reduced.

The internal latent image type silver halide emulsion which can be preferably used in the light-sensitive material of the present invention is particularly preferably transparent so that the coated silver amount is in the range of about 1 to 3.5 g / m ^2. A part of the sample applied to the support is
Exposure to the light intensity scale for a predetermined period of time up to 1 second, using the following surface developer A, which develops only the surface image of the grains substantially free of the silver halide solvent, uses
When developed at 4 ° C. for 4 minutes, another part of the same emulsion sample is also exposed to light and develops an image inside the grains. This is an emulsion showing the maximum density not more than 1/5 of the density.
More preferably, the maximum density obtained with surface developer A is not greater than 1/10 of the maximum density obtained with internal developer B.

(Surface developer A) Methol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water was added to 1000 cc (internal developer B) Methol 2 0.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5.0g Potassium iodide 0.5g 1000 cc with water added to the photosensitive material of the present invention The internal latent image type silver halide emulsion used includes those prepared by various methods. For example, a conversion type silver halide emulsion described in U.S. Pat. No. 2,592,250 or described in U.S. Pat. Nos. 3,206,316, 3,317,322 and 3,367,778. Silver halide emulsions having internally chemically sensitized silver halide grains, or US Pat. Nos. 3,271,157 and 3,447,927
Having silver halide grains containing polyvalent metal ions described in U.S. Pat. No. 3,531,291 or halogen containing a dopant described in U.S. Pat. No. 3,761,276. Silver halide emulsions in which the grain surfaces of silver grains are weakly chemically sensitized, or JP-A-50-8524;
Nos. 50-38525 and 53-2408, silver halide emulsions comprising grains having a laminated structure, and others, JP-A-52-156614 and JP-A-55-156614.
No. 127549, and the like.

The silver halide grains used in the light-sensitive material are cubic, octahedral, tetrahedral composed of a mixture of (100) and (111) planes, shapes having a (110) plane,
Any of a spherical shape and a flat shape may be used. The average particle size is 0.
Those having a thickness of from 0.5 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having a uniform grain size and crystal habit or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having a uniform grain size and crystal habit It is preferred that

In the present invention, it is preferable to use a monodisperse silver halide emulsion. Monodisperse silver halide emulsions are those in which the weight of silver halide contained within a grain size range of ± 20% around the average grain size rm is 60% or more of the total weight of silver halide grains. Preferably at least 70%,
It is more preferably at least 80%. Here, the average particle size r
m is the product ni × ri ³ is defined as a grain size ri when the maximum (three significant figures, the minimum digit is ON 4 Discard 5) of the frequency ni and ri ³ particles having a particle size ri . The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains having a shape other than spherical. . The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter or the area at the time of projection on the print (the number of measured particles is zero). Discrimination must be 1000 or more).

Particularly preferred monodisperse emulsions have a distribution width defined by the following formula of 20% or less.

(Particle size standard deviation / average particle size) × 100 = width of distribution (%) Here, the average particle size and the particle size standard deviation are determined from ri defined above.

The monodispersed emulsion was prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to a pAg solution in a gelatin solution containing seed particles.
And controlled pH and addition by the double jet method. In determining the addition rate, JP-A-54-48521 and JP-A-58-49938 can be referred to. Further, as a method for obtaining a monodisperse emulsion, a growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied. or,
It is also preferable to add two or more of the monodispersed emulsions to the same color-sensitive layer.

The size of the silver halide particles in each emulsion layer of the light-sensitive material can be in a wide range in consideration of the required properties, in particular, various characteristics such as sensitivity, sensitivity balance, color separation, sharpness, and granularity. Can be determined from within.

In the present invention, a step of exposing a color photosensitive material to produce a color proof based on halftone image information composed of color-separated yellow image information, magenta image information, cyan image information and black image information. In at least a part of the halftone dot image information, halftone dot information is converted such that the number of halftone dots per inch ² is 2 × 10 ⁵ or more when the halftone dot area ratio is 40%. Can be used. It is preferably 3 × 10 ⁵ or more, more preferably 4 × 10 ⁵ to 2 × 10 ⁶ . The number of the halftone dots can be measured by counting halftone images taken by an optical microscope or the like.

The dot image information used in the present invention is a dot image recorded on a film, and it is preferable to perform exposure by scanning the light source with the film in close contact with the photosensitive material. , Commonly used A
This is particularly effective in the case of a dot image for high-definition printing by the M screening method. The present invention is also effective in the case of a dot image formed by a frequency-modulated screening method called a so-called FM screen method.

When the light-sensitive material of the present invention is processed with a color developing solution, the color developing solution, the bleach-fixing solution and the stabilizing solution are respectively a replenishing developer, a replenishing bleaching solution, a replenishing fixing solution and a replenishing bleach-fixing. The developing process can be continuously performed while replenishing the solution, the replenishing stabilizing solution and the like.

It is preferable to include a fluorescent whitening agent in the light-sensitive material and / or the processing solution of the present invention in order to improve the white background.

The developer used in the present invention may further contain a specific antifoggant and a development inhibitor, or these additives may be arbitrarily incorporated into the constituent layers of the light-sensitive material. It is possible.

Further, known photographic additives can be used in the light-sensitive material of the present invention.

Known photographic additives (chemical sensitizer, spectral sensitizing dye, development accelerator, antifoggant, stabilizer, color stain inhibitor, image stabilizer, ultraviolet absorber, filter dye, brightener Hardeners, coating aids, surfactants, plasticizers, slip agents, antistatic agents, matting agents, binders), for example, RD17643, page 23, paragraphs III to 29, XXI
Item, RD18716, pages 648 to 651, RD3081
19, 996, pages III-A, pages 10-12, pages XXI-E.

Next, a color image forming method using the color photographic light-sensitive material of the present invention will be described. Various exposure means can be used for exposing the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as an illumination light source or a writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom-filled lamps, mercury lamps, fluorescent lamps and strobe or metal burning flash bulbs, semiconductor lasers, light emitting diodes, and plasma light sources can also be used as recording light sources. A phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like;
Exposure means in which a linear or planar light source is combined with a micro shutter array using liquid crystal (LCD) or lanthanum-doped lead zirconate titanate (PLZT) can also be used. If necessary, a spectral distribution used for exposure can be adjusted by a color filter. In particular, gas lasers (He-Ne laser, Ar laser, He-C
exposure using a so-called scanning exposure method (scanner method) in which a high-density beam light such as various lasers such as a d-laser) or a semiconductor laser is used as a light source, and the image is exposed by moving the light relative to a photosensitive material. Means are preferred for exposing the light-sensitive material of the present invention. In the case of exposure by the scanning exposure method, the time required for exposing the silver halide is the time required for exposing a small area.
As the minute area, a minimum unit for controlling the light amount from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of the pixel. The size of this pixel depends on the pixel density, and a practical range is 50 to 2000 dpi. In the color photographic light-sensitive material of the present invention, the pixel density is 40
When the pixel size is 0 dpi, the pixel size is 1 pixel.
The exposure time to the pixel is 10 ^-3 seconds or less (preferably 10 ^-6 seconds)
Scan exposure under the condition of ( ^{−10 −4} s).

Although the color photographic light-sensitive material of the present invention has various uses, it is suitable for producing color prints, color copies and color proofs. As the method for producing a color proof of the present invention, a conventional method for producing a color proof can be used except for using the color photographic light-sensitive material of the present invention as described above. That is, according to the most preferred embodiment of the present invention,
The method for producing a color proof according to the present invention includes the steps of: performing color separation and halftone image conversion on the color photographic light-sensitive material of the present invention; a yellow halftone dot image film, a magenta halftone dot image film, a cyan halftone dot image film, and black ink; This is a method in which a halftone dot image film is used and sequentially exposed to infrared light, blue light, red light, and green light, and then color-developed as described above to form a color image.

[0134]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Emulsion EM-P1 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide were simultaneously produced by a control double jet method. Addition, particle size 0.25μ
m cubic silver bromide core emulsion was obtained. At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 50: 50) were simultaneously added to the obtained core emulsion by a control double jet method. The shell was formed until the average particle size became 0.42 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

After washing with water to remove water-soluble salts, gelatin was added to obtain EM-P1. The distribution width of this emulsion EM-P1 was 8%.

<< Preparation of Emulsion EM-P2 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5 by molar ratio). ) Was added simultaneously by the control double jet method to obtain a cubic silver chlorobromide core emulsion having a particle size of 0.18 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

To the obtained core emulsion, an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added by a control double jet method. The shell was formed until the average particle size became 0.25 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

After washing with water to remove water-soluble salts, gelatin was added to obtain EM-P2. The distribution width of this emulsion EM-P2 was 8%.

<Preparation of Blue-Sensitive Silver Halide Emulsion> Emulsion E
After sensitizing dye BS-1 was optimally sensitized by adding sensitizing dye BS-1 to M-P1, 100 mg of T-1 was added per mol of silver to prepare blue-sensitive emulsion EM-B1.

<Preparation of Green-Sensitive Silver Halide Emulsion> Emulsion E
A green-sensitive emulsion EM- was prepared in the same manner as the blue-sensitive emulsion EM-B1 except that the sensitizing dye GS-1 was added to M-P1 to optimize the color sensitization.
G1 was produced.

<Preparation of Red-Sensitive Silver Halide Emulsion> Emulsion E
A red-sensitive emulsion EM-R1 was prepared in the same manner as the blue-sensitive emulsion EM-B1, except that sensitizing dyes RS-1 and RS-2 were added to MP-P2 to optimize the color sensitization.

<Preparation of Infrared-sensitive Silver Halide Emulsion> The emulsion EM-P2 was optimally sensitized by adding a sensitizing dye IRS-1, and the blue-sensitive emulsion EM-B1 was added except that AF-1 was added. In the same manner as in the above, an infrared-sensitive emulsion EM-IR1 was prepared. E
The spectral sensitivity maximum of M-IR1 is 765 nm.

AF-1; 1-phenyl-5-mercaptotetrazole T-1; 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene

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A high-density polyethylene was laminated on one side and a molten polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by weight was laminated on the other side.
The EM-B1, EM-G1, EM-R1, and EM- on a 10 μm paper pulp reflective support (containing a small amount of colorant).
Using each emulsion of IR1, each layer having the following constitution was coated on the side of the polyethylene layer containing titanium oxide, and further, 7.2 g / m ² of gelatin and 0.2 g of silica mat material were formed on the back side.
A multilayer silver halide color photographic light-sensitive material 101 coated with 65 g / m ² was prepared. The coating amount is (g /
m ² ). H-1 and H-2 were added as hardeners. Surfactant S as coating aid and dispersing aid
U-1, SU-2, and SU-3 were added and prepared.

SU-1: sodium sulfosuccinate di (2-ethylhexyl) ester SU-2: sulfosuccinate di (2,2,3,3,4,4)
Sodium 5,5-octafluoropentyl) ester SU-3: Sodium tri-i-propylnaphthalenesulfonate H-1: 2.4-Dichloro-6-hydroxy-2-triazine sodium H-2: Tetrakis (vinylsulfonyl) Methyl) methane Each layer having the following composition was applied.

12th layer (ultraviolet absorbing layer) Gelatin 1.20 Ultraviolet absorbing agent (UV-1) 0.07 Ultraviolet absorbing agent (UV-2) 0.02 Ultraviolet absorbing material (UV-3) 0.07 Silica mat Agent 0.01 11th layer (blue-sensitive layer) gelatin 0.92 blue-sensitive emulsion (EM-B1) 0.33 magenta coupler (M-1) 0.20 yellow coupler (Y-3) 0.05 inhibitor ( T-1) 0.002 Inhibitor (T-2, T-3, T-4) (molar ratio 1: 1: 1) 0.0004 Stain inhibitor (HQ-1) 0.03 High boiling solvent (SO -1) 0.31 Tenth layer (intermediate layer) Gelatin 0.40 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.01 High boiling solvent (SO-2) 0.005 9th layer (yellow colloid layer) Gelatin 0.08 a Low colloid silver 0.09 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.01 High boiling solvent (SO-2) 0.005 Polyvinylpyrrolidone 0.04 Eighth layer (intermediate layer) ) Gelatin 0.04 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.01 High boiling solvent (SO-2) 0.005 7th layer (green sensitive layer) Gelatin 1.20 Green-sensitive silver chlorobromide emulsion (EM-G1) 0.38 Yellow coupler (Y-1) 0.51 Magenta coupler (M-1) 0.11 High boiling solvent (SO-3) 0.31 Stain inhibitor ( HQ-1) 0.06 inhibitor (T-1) 0.004 inhibitor (T-2, T-3, T-4) (molar ratio 1: 1: 1) 0.0002 6th layer (intermediate layer) ) Gelatin 0.50 Stain inhibitor (HQ-2) 4 Antistain agent (HQ-3) 0.02 High boiling point solvent (SO-2) 0.01 Fifth layer (cyan layer) Gelatin 1.75 Red-sensitive silver chlorobromide emulsion (EM-R1) 0.25 Green Sensitive silver chlorobromide emulsion (EM-G1) 0.24 Cyan coupler (EC-1) 0.31 High boiling solvent (SO-4) 0.33 High boiling solvent (SO-5) 0.33 Stain inhibitor ( HQ-1) 0.035 Inhibitor (T-1) 0.0015 Inhibitor (T-2, T-3, T-4) (molar ratio 1: 1: 1) 0.0004 Fourth layer (intermediate layer) ) Gelatin 0.70 Stain inhibitor (HQ-2) 0.04 Stain inhibitor (HQ-3) 0.02 High boiling point solvent (SO-2) 0.01 Anti-irradiation dye (AI-1) 0.03 Anti-irradiation dye (AI-2) 0.03 Third layer (infrared layer) Zera 1.10 Infrared photosensitive emulsion (EM-IR1) 0.40 Yellow coupler (Y-1) 0.43 Yellow coupler (Y-2) 0.10 High boiling point solvent (SO-1) 0.43 Stain prevention Agent (HQ-1) 0.05 Inhibitor (T-1) 0.006 Inhibitor (T-2, T-3, T-4) (molar ratio 1: 1: 1) 0.0004 Second layer ( Intermediate layer) Gelatin 0.40 Anti-stain (HQ-2) 0.01 Anti-stain (HQ-3) 0.005 High boiling solvent (SO-2) 0.003 Anti-irradiation dye (AI-4) 0 .05 First layer (antihalation layer) Gelatin 0.60 Black colloidal silver 0.03 Polyvinylpyrrolidone 0.10 * The coverage of the silver halide emulsion was shown in terms of silver.

SO-1: tri (n-octyl) phosphine oxide SO-2: di (i-decyl) phthalate SO-5: tricresyl phosphate HQ-1: 2,5-di (t-butyl) Hydroquinone HQ-2: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5-di-sec- A mixture of tetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone in a weight ratio of 1: 1: 2 T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-3: N- Benzyl adenine T-4: 2-mercaptobenzothiazole

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[0154]

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Further, Samples 102 to 110 were prepared in the same manner as in Sample 101 except that the compound represented by the general formula (I) of the present invention shown in Table 1 was added to the third layer of Sample 101 at 6 mol%. did.

As the halftone dot original, an original prepared on a screen having halftone dots of 300 lines per inch was used.
A manuscript prepared by a so-called FM screening method in which one halftone dot is approximately 20 μm was also used. In addition,
When the dot area ratio is 40%, the number of dots per inch ² is 90 × 103 for the former manuscript and 6 for the latter manuscript.
The number was 45 × 103.

Each of the samples 101 to 110 obtained as described above was exposed by bringing the prepared halftone dot original into close contact with the sample under the following conditions. For yellow, the yellow plate was brought into close contact with the sample, and the exposure condition -Y shown below was used.
For magenta, the magenta plate was brought into close contact with the sample and exposed under the following exposure conditions -M, and for cyan, the cyan plate was brought into close contact with the sample and exposed under the following exposure conditions -C. The black plate was similarly brought into close contact with the sample and exposed under the following exposure conditions -K. Each of the exposed light-sensitive materials was processed by the following developing process to obtain a dye image consisting of halftone dots.

(Exposure condition-Y) Each light-sensitive material was exposed to light using an infrared light source through an infrared light-transmitting filter (LEE filter, 026 and 363), and the ND filter density was further reduced. The exposure was adjusted by adjusting the ND filter density so that the dot area of the 40% yellow dot original document area after development was 40%. The exposure time is 0.3 seconds.

(Exposure condition-M) Each photosensitive material was exposed to light using a white light source through a blue filter (Watten No. 47B), and the density of the ND filter was further adjusted to obtain a 40% net of magenta after development processing. The exposure amount was adjusted with the ND filter density so that the dot area of the dot document portion became 40%. The exposure time is 0.3 seconds.

(Exposure condition-C) Each photosensitive material was exposed to light using a white light source through a red filter (Ratten No. 26), and the ND filter density was further adjusted.
The halftone dot area of the 40% halftone original portion of cyan after development processing is 4
The exposure amount was adjusted at each ND filter density so as to be 0%. The exposure time is 0.3 seconds.

(Exposure condition-K) Each photosensitive material was exposed to light using a white light source through a green filter (Watten No. 58), and the density of the ND filter was further adjusted.
The exposure amount was adjusted with the ND filter density so that the halftone dot area of the 40% halftone original after development was 40%. The exposure time is 0.3 seconds.

As the infrared light source used for the exposure condition -Y, an infrared fluorescent lamp for irradiating infrared light was used. As the white light source used for the exposure conditions -M, C, and K, a daylight fluorescent lamp was used.

Next, processing was performed according to the following processing step-1 (new liquid processing) to obtain a dye image consisting of halftone dots. However, for fog exposure, the thickness was 3 mm while immersed in the developing solution.
The entire surface of the photosensitive material was uniformly exposed to light through a layer of a developing solution having a thickness of 2 mm.

(Processing step-1) Processing step Temperature Time Immersion (developer) 37 ° C for 12 seconds Fog exposure -12 seconds Development 37 ° C for 95 seconds Bleaching and fixing 35 ° C for 45 seconds Stabilization processing 25-30 ° C for 90 seconds Drying 60- 85 ° C. for 40 seconds Color developer composition Benzyl alcohol 15.0 ml Ceric sulfate 0.015 g Ethylene glycol 8.0 ml Potassium sulfite 2.5 g Potassium bromide 0.6 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-10 0.1 g hydroxylamine sulfate 5.0 g sodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Optical brightener (4,4′-diaminostilbene) Disulfonic acid derivative) 1.0 g potassium hydroxide 2.0 g diethylene glycol Add 15.0 ml water to make the total volume 1000 ml and adjust to pH 10.15.

Composition of bleach-fixing solution Ferric ammonium diethylenetriaminepentaacetate 90.0 g Diethylenetriaminepentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1,2 , 4-triazole 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to make the total volume 1000 ml.

Stabilizing solution composition o-phenylphenol 0.3 g potassium sulfite (50% aqueous solution) 12.0 ml ethylene glycol 10.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g zinc sulfate Heptahydrate 0.7 g ammonium hydroxide (28% aqueous solution) 2.0 g polyvinylpyrrolidone (K-17) 0.2 g fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g The total volume is made up to 1000 ml and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

Note that the stabilization treatment was of a countercurrent type having a two-tank configuration.

Further, each sample was exposed under exactly the same conditions as in the case of the processing with the new solution, and processed in the same manner as in the processing step 1. However, the amount of the developing replenisher replenished with the developing solution in the processing step 1 was reduced. Until the developing tank became three times as large as the developing tank, a developing process using a developing solution, a bleach-fix solution and a stabilizing solution obtained by performing the continuous process on the sample 101 was also performed (continuous process).

The formula of the replenisher for performing the running process is shown below.

(Color developing replenisher) Benzyl alcohol 18.5 ml Ceric sulfate 0.015 g Ethylene glycol 10.0 ml Potassium sulfite 2.5 g Potassium bromide 0.3 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g hydroxylamine sulfate 5.0 g sodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4 g fluorescent whitening agent (4,4′-diamino (Stilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Water is added to adjust the total volume to 1 liter, and the pH is adjusted to 10.35.

(Bleach-fixing solution replenisher) Same as the bleach-fixing solution.

(Stabilizing solution replenisher) Same as the above stabilizing solution.

The replenishment amount was 320 ml per m ^{2 of} the light-sensitive material for the development replenisher, the bleach-fixer and the stabilizer.

Konsensus 570 manufactured by Konica Corporation
Was used to produce a color proof consisting of halftone images. Processing was continued until the total amount of the replenished color developing replenisher was three times the amount of the color developing tank.

A 40% dot number 90 × 103 / inch ² dot manuscript produced by the above-described screen method consisting of 300 dots per inch, and a 645 × 103 dot produced by the FM screening method. / Inch
^For each of the halftone originals of No. ² and the images obtained in the new liquid processing and the continuous processing, the yellow halftone quality of 40% of the images was visually evaluated by loupe observation.
Scored out of perfect scores. The halftone dot quality is relatively scored with 5 being the best and 1 being the worst. Also, the number of 40% halftone dots produced by a screen method consisting of 300 halftone dots per inch is 90 × 10
The approximation between the hue of the image portion of the single color yellow and the printing ink using the halftone dot document of 3 pieces / inch ² was visually evaluated at the same time, and scored out of 5 points. However, the degree of approximation of the color tone was relatively scored, with 5 being the best and 1 being the poorest.

Furthermore, a new liquid using a halftone dot manuscript having a dot count of 90 × 103 / inch ² , prepared by a screen method comprising 300 halftone dots per inch, of each of the processed samples. High temperature (5
It was left in an atmosphere of 5 ° C., 40% RH) and high humidity (40 ° C., 80% RH) for 14 days, and the heat resistance and humidity resistance of the yellow dye image were examined. However, the heat resistance and the moisture resistance of the dye image were also evaluated by visually observing the halftone dot quality of 40% of the image obtained in the new liquid treatment by loupe observation, and the best one was set to 5, and the worst was set. The score was relatively high, with 1 being the score of 1. Table 1 shows the results.

[0177]

[Table 1]

As is clear from Table 1, the yellow dye image of the sample of the present invention obtained by a screen consisting of halftone dots of 300 lines per inch and by a film screen-resolved by the FM screening method is contained in the third layer. By adding the compound of the present invention, it is possible to obtain a color image which is more excellent in halftone dot quality, has a color tone similar to that of a printing ink, and is stable even after repeated development processing. Also, with respect to heat resistance and moisture resistance, a stable color image can be obtained by adding the compound of the present invention to the third layer.

Example 2 Em-B1, Em-G1, Em-R1, and Em-IR
ExZK- as a nucleating agent in each photosensitive layer using each emulsion of Example 1.
1 and ExZK-2 with respect to silver halide were 10
^-3 , 10 ^-2 % by weight, Cpd-1,2,
3 was used in an amount of 10 ^-2 % by weight. Further, for each layer, alkanol XC (Dupont) and sodium alkylbenzene sulfonate were used as emulsifying and dispersing aids, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-4, 5, 6) was used as a stabilizer in the layer containing silver halide and colloidal silver. Except that the above nucleating agent, nucleation accelerator, emulsifying and dispersing aid, coating aid, and stabilizer were newly added, the multilayer color photosensitive material sample 20 was prepared in the same manner as the sample 101 prepared in Example 1.
1 was produced.

Further, the compound of the general formula (I) of the present invention shown in Table 2 was added to the third layer of Sample 201 in the form of a 6-mo yellow coupler.
Sample 202 was prepared in the same manner as Sample 201 except that 1% was added.
To 207 were produced.

ExZK-1; 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate ExZK-2; 2- [ 4- {3- [3- {3- [5-
{3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4
-Hydroxy-1-naphthylthio {tetrazole-1-
Yl] phenyl {ureido] benzenesulfonamide}
Phenyl] -1-formylhydrazine

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In the same manner as in Example 1, the samples 201 to 207 obtained as described above were exposed to a yellow plate of a halftone dot original document in contact with the sample under the exposure condition -Y. The plate was brought into close contact with the sample and exposed under exposure conditions -M, the cyan plate was brought into close contact with the sample, exposed under exposure conditions -C, and the black plate was brought into close contact with the sample and exposed under the following exposure conditions -K. Each of the exposed light-sensitive materials was processed by the following developing process to obtain a dye image consisting of halftone dots.

Next, processing was performed according to the following processing step-2 (new liquid processing) to obtain a dye image consisting of halftone dots.

(Processing step-2) Processing step Temperature Time Color development 38 ° C 135 seconds Bleaching and fixing 34 ° C 40 seconds Rinse with water (1) 32 ° C 40 seconds Rinse with water (2) 32 ° C 40 seconds Dry 80 ° C 30 seconds Replenish water The system was a so-called countercurrent replenishment system in which the washing bath (2) was replenished, and the overflow of the washing bath (2) was led to the washing bath (1).

The composition of each processing solution is as follows.

[Color developing solution] [Tank solution] [Replenisher] D-Sorbit 0.15 g 0.20 g Sodium naphthalene sulfonate / formalin condensate 0.15 g 0.20 g Nitrilotris (methylene phosphonic acid) pentasodium salt 1 0.8 g 1.8 g diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 13.5 ml 18.0 ml potassium bromide 0 0.70 g-benzotriazole 0.003 g 0.004 g sodium sulfite 2.4 g 3.2 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.0 g 10.6 g triethanolamine 6.0 g 8.0 g N -Ethyl- N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 6.0 g 8.0 g potassium carbonate 30.0 g 25.0 g Fluorescent brightener (diaminostilbene type) 1.3 g 1.7 g Add water 1000 ml 1000 ml pH (25 ° C.) (pH adjusted with KOH or sulfuric acid) 10.30 10.79 Composition of bleach-fix solution (same for tank solution and replenisher) Ethylenediaminetetraacetic acid ・ 2 Sodium dihydrate 4.0 g Ethylenediaminetetraacetic acid / Fe (III) ammonium dihydrate 55.0 g Ammonium thiosulfate (750 g / liter) 168 ml Sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-mercapto -1,3,4-triazole 0.5 g ammonium nitrate 10.0 g water In addition 1000ml pH (25 ° C) (pH adjusted with ammonia water or acetic acid) 6.5 Rinse water (same as tank solution and replenisher) Chlorinated sodium isocyanurate 0.02g Deionized water (conductivity 5μs / cm or less) ) 1000 ml pH 6.5 Each sample subjected to exposure was evaluated by processing with a new solution using a color developing solution according to Processing Step-2. Further, each sample was exposed under exactly the same conditions as in the case of the new liquid processing, and the processing step-2
The processing was performed in the same manner, but the developing solution in the processing step-2 was replenished until the total amount of the replenished developing replenisher became three times the developing tank.
A developer obtained by performing continuous processing on the sample 201,
Development processing (continuous processing) using a bleach-fixing solution and a stabilizing solution was also performed, and evaluation of yellow dot quality was performed in the same manner as in Example 1. However, the halftone dot quality was relatively scored with 5 being the best and 1 being the worst.

Also, as in the first embodiment, 3
40 produced by a screen method consisting of halftone dots of 00 lines
The hue of the image portion of a single yellow color and the degree of approximation to the printing ink using a halftone original having a dot count of 90 × 103 / inch ² were visually evaluated at the same time, and scored out of 5 points. However, the degree of approximation of the color tone was relatively scored, with 5 being the best and 1 being the poorest.

Further, a 40% dot count of 90 × 103 dots / inch ² prepared by the above-described screen method consisting of 300 dots per inch was obtained by a new liquid treatment. Heat the treated sample to a high temperature (55 ° C, 4
0% RH), 1 in a high humidity (40 ° C, 80% RH) atmosphere.
After standing for 4 days, the yellow dye image was examined for heat resistance and moisture resistance. The heat resistance and the moisture resistance of the dye image were evaluated by visual observation of the dot quality at 40% of the image obtained by the new liquid treatment by loupe observation.
The worst score was 1 and the score was relatively high. Table 2 shows the results.

[0190]

[Table 2]

From the results shown in Table 2, the yellow dye image of the sample of the present invention obtained from the two screen-decomposed screen films can be further improved in dot quality by adding the compound of the present invention to the third layer. It can be seen that the color image is excellent and has a color tone similar to that of the printing ink, and a stable color image can be obtained even after repeated development processing. In addition, heat resistance and moisture resistance are also third.
By adding the compound of the present invention to the layer, a stable color image can be obtained. Example 3 Table 5 shows the cyan coupler of the fifth layer of the sample 101 of Example 1.
In the same manner as in Sample 101 except that 6 mol% of the cyan coupler of the present invention shown in Table 3 was added to the fifth layer of Sample 101. Was prepared.

The samples 301 to 300 obtained as described above
10 was subjected to the same exposure and development processing as in Example 1, and then the evaluation of the halftone dot quality of the cyan image was performed as in Example 1. However, the halftone dot quality was relatively scored with 5 being the best and 1 being the worst.

The similarity of the color tone was evaluated in the same manner as in Examples 1 and 2. Further, the treated sample similar to the above is subjected to high temperature (55 ° C., 40% RH) and high humidity (40 ° C., 80%).
% RH), and the heat resistance and the moisture resistance of the cyan dye image were examined. However, the heat resistance and humidity resistance of the dye image are 40% of the image obtained in the new liquid processing.
The halftone dot quality of a point was visually evaluated by loupe observation, and the best one was set to 5, and the worst one was set to 1, which was relatively scored out of 5 points. Table 3 shows the results.

[0194]

[Table 3]

From the results shown in Table 3, the cyan dye images obtained from the two screen-decomposed screen films were as follows:
By adding the compound of the present invention to the fifth layer, the halftone dot quality is excellent, and the color tone is very similar to the printing ink,
It can be seen that a stable color image can be obtained even after repeated development processing.

Example 4 As a light source, a helium-neon gas laser (wavelength 63
3 nm and 543 nm) and an argon laser (wavelength 458 nm) at a pitch of 100 μm and a diameter of 80 μm.
An apparatus capable of sequentially performing scanning exposure (substantially about 5 × 10 ⁻⁵ seconds) on a sample while assembling a luminous flux of 1.6 m / s with a scanning exposure of 1.6 m / s perpendicular to the scanning direction was assembled. Using this apparatus, area gradation exposure was performed for sensitometry, and development processing was performed in the same manner as in Example 1. When the same evaluation as in Example 1 was performed, the light-sensitive material of the present invention similarly had good yellow image color reproducibility.

[0197]

According to the present invention, a silver halide color photographic light-sensitive material having excellent halftone dot reproducibility, being stable against fluctuations in processing solutions, and having excellent image fastness, especially heat resistance, moisture resistance and color reproducibility. , A processing method, an image forming method, and a method for producing a color proof.

Claims (7)

[Claims] 1. A halogenated composition comprising at least one black image information forming silver halide emulsion layer on a support and at least one compound represented by the following general formula (I). Silver color photographic light-sensitive material. Embedded image [In the formula, Cp represents a coupler residue, SOL represents a solubilizing group, n represents an integer of 1 to 3, and Ball represents a diffusion resistance which can be eliminated during a coupling reaction with an oxidized form of a color developing agent. Represents a group. ] 2. The silver halide color photographic material according to claim 1, which contains at least one coupler represented by the following general formula (II). Embedded image [Wherein, R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, m represents an integer of 0 to 2, and when m is 0, R ¹ represents an electron-withdrawing group; When 1 or 2, at least one of R ¹ and R ² represents an electron-withdrawing group, and when m is 2, a plurality of R ² may be the same or different, and bond to each other to form a ring May be. X represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized form of a color developing agent. Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the heterocyclic ring may be further bonded to a benzene ring or the like. ] 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the material contains at least one silver halide emulsion layer containing internal latent image type silver halide grains. 4. The method according to claim 1, wherein the silver halide emulsion layer contains at least one silver halide emulsion layer containing internal latent image type silver halide grains formed by a nucleating agent. 3. The silver halide color photographic light-sensitive material according to item 1. 5. A silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material according to claim 1 is subjected to image exposure and then to uniform exposure over the entire surface to carry out fog processing. Processing method. 6. An image forming method comprising: exposing the silver halide color photographic material according to claim 1 to a laser light source; developing; and forming an image. 7. A method for producing a color proof, comprising forming a halftone image using the silver halide color photographic light-sensitive material according to claim 1.