JPH0829932A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide photosensitive material for color proof which has color tone similar with a printing ink, remarkably excellent whiteness, and suitability for continuous processing at the time of producing a color proof and moreover which has excellent stability of the photosensitivity with the lapse of time by containing a specified acylacetoamide-type yellow coupler together with a specified high boiling point organic solvent. CONSTITUTION:An acylacetoamide-type yellow coupler containing a group having a formula I is contained together with a high boiling point organic solvent having a formula II. In the formula R1, R2, and R3 stands for a substituent and at least one of the substituent groups expressed as R1, R2, and R3 is a halogen atom, an electron attractive group, or a group substituted with a halogen atom or an electron attractive group. In the formula II, R4, R5, and R6 stand for a substituent and l, m, and n stand for an integer 0 or 1. It is preferable that one of R1, R2, and R3 is a halogen atom or a group substituted with a halogen atom and it is especially preferable that one of them is fluorine atom or a fluoroalkyl group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is preferably used for preparing a proof color image (color proof) from a plurality of halftone dot image information obtained by color separation and halftone image conversion in a color plate making / printing process. The present invention relates to a silver halide color photographic light-sensitive material that can be used.

[0002]

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

The overlay method is very simple and inexpensive to produce, and has the advantage that it can be used for proofreading by simply stacking four color (subtractive primary colors and black) film sheets. There is a drawback in that the overlapping produces gloss, which results in a texture different from that of the printed matter.

In the surprint method, a colored image is superposed on one support, and a method of obtaining a colored image by toner development utilizing the adhesiveness of a photopolymerizable material is disclosed in US Pat. No. 3,582,327. Nos. 3,607,264 and 3,620,726.

Further, a color proof is formed by transferring a photosensitive coloring sheet to a support, forming an image by exposure and development, laminating another coloring sheet thereon, and repeating the same process. The method of creating is 47
-27441 and JP-A-56-501217.

Further, a method is known in which a photosensitive colored sheet is used and each colored image obtained by exposing and developing the corresponding color separation film is transferred and formed on one support.
-Known as No. 97140. As the colorant of the toner and the color sheet for forming these images, the same coloring material as the printing ink can be used, and thus the color tone of the obtained color proof becomes similar to that of the printed matter.

However, these methods have the drawbacks that images must be superposed or transferred in the process of producing a color proof, which requires a long operation time and a high manufacturing cost.

As a solution to these drawbacks, a method for producing a color proof using a silver salt color photographic light-sensitive material having a white support is disclosed in JP-A-56-113139 and JP-A-5-113139.
6-104335, 62-280746, 62-280747, 62-280
No. 748, No. 62-280749, No. 62-280750, No. 62-280849, etc.

In this method, a color-separated black-and-white halftone image composed of a plurality of sheets converted from a color original into a halftone image which has been color-separated is sequentially printed on one sheet of color paper by a method such as contact printing to develop color. Upon application, a color image formed imagewise imagewise from the coupler-formed dye is used as a proofing image.

However, in this technique, since a color image formed by a dye formed from a coupler in an imagewise manner is used as a proof image, it is difficult to obtain an image having a color tone close to that of a color image obtained from printing ink. It has the drawback of being.

Since the absorption characteristics of the dye image obtained are very important for color reproduction, research into couplers having good absorption characteristics has recently been actively conducted.

For example, JP-A-63-123047 and JP-A-4-9051
No. 4-124661, a pivaloylacetanilide yellow coupler having an alkoxy group in the anilide portion,
4-174428, 4-184434, 5-11416 and the like disclose asymmetric malondiamide yellow couplers and the like, but it is said that all are sufficient for solving the above problems. It is difficult and needs further improvement.

A technique for producing a color proof by using a silver salt color photographic light-sensitive material having a white support includes
When the color image is approximated to the printed matter, the density of the black image such as characters is insufficient compared to the printed matter, and if the means for increasing the density to approximate the density of the black image such as characters to the printed matter is taken, the color image of the printed matter However, there is a drawback in that it is difficult to satisfy both of them.

As a technique for improving this drawback, in addition to the yellow coloring layer, the magenta coloring layer, the cyan coloring layer,
A technique of providing a fourth black plate layer having a spectral sensitivity different from any of the layers is conventionally known. For example, JP-A-3-122637 discloses a technique using four types of image forming layers of yellow, magenta, cyan and black. In addition, JP-A-2-2898
No. 46, No. 2-183251, etc. also disclose a technique for improving this problem, but in both cases, the number of exposures increases and productivity is impaired, and image stability is lacking. Further improvement is required for the use.

After shipment of the silver halide photographic light-sensitive material,
When a color proof is created using a silver halide photographic light-sensitive material that has been stored for a long period of time, the color density after exposure and processing, especially the yellow color image, will be There is also a problem that the color density obtained by the color proof created by the above method is considerably deteriorated as compared with the color density of the yellow image, and further the white background is also deteriorated.

[0016]

Therefore, an object of the present invention is to prepare a color proof from halftone image information obtained by color separation and halftone image conversion using a silver halide photographic light-sensitive material. It is an object of the present invention to provide a color proof light-sensitive material having a color tone similar to that of a printing ink, an extremely excellent white background, and compatibility with continuous processing, and further having excellent stability over time of the light-sensitive material.

[0017]

The above object of the present invention has been achieved by the following constitution.

(1) A halogen characterized in that an acylacetamide type yellow coupler having a group represented by the following general formula [I] is contained together with a high-boiling organic solvent represented by the following general formula [II]. Silver halide photographic light-sensitive material.

[0019]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ represent a substituent,
At least one of the substituents represented by R ₁ , R ₂ and R ₃ represents a halogen atom, an electron-withdrawing group, or a group in which a halogen atom or an electron-withdrawing group is substituted.

[0021]

[Chemical 4]

In the formula, R ₄ , R ₅ and R ₆ represent a substituent,
l, m and n represent an integer of 0 or 1.

(2) R ₁ , R in the general formula [I]
_The silver halide photographic light-sensitive material as described in the above item (1), wherein at least one of the substituents represented by ₂ and R ₃ is a halogen atom or a group substituted with a halogen atom.

(3) Exposure and processing are carried out based on the halftone dot image information consisting of the color-separated yellow color image information, magenta image information, cyan color image information and black color image information to obtain a yellow color image, a magenta color image, The silver halide photographic light-sensitive material as described in (1) or (2) above, which forms a cyan color image to form a color proof.

The present invention will be described in more detail below.

In the general paper [I], R ₁ , R ₂ and R ₃
The substituent represented by is a linear or branched alkyl group (for example, methyl group, ethyl group, i-propyl group, t-butyl group, dodecyl group, i-hexylnonyl group, etc.), cycloalkyl group (for example, Cyclopropyl group, cyclohexyl group, bicyclo [2,2,1] heptyl group, adamantyl group, etc.), aryl group (eg, phenyl group, 1-naphthyl group,
9-anthranyl group etc.), heterocyclic group (eg 3-indolyl group, 2-thiophenyl group, 4-imidazolyl group etc.), halogen atom (eg fluorine, chlorine, bromine, iodine etc.), and electron-withdrawing group (eg Halogenated alkyl group, halogenated aryl group, cyano group, carbamoyl group, acyl group,
An acyloxy group, an oxycarbonyl group, a nitro group, a nitroso group, a sulfonyl group, a sulfonyloxy group, a sulfamoyl group, a phosphonyl group, a phosphonyloxy group, etc., and a substitution represented by R ₁ , R ₂ and R _3. The base is
Further, it may have a substituent, and as the substituent, R ₁ ,
A group having the same meaning as the substituent represented by R ₂ and R ₃ , an alkenyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a sulfonylamino group, a sulfamoylamino group, an acylamino group, and a heterocyclic oxy group. , Urethane groups, ureido groups and the like, and at least one of R ₁ , R ₂ and R ₃ is a halogen atom, an electron-withdrawing group, or a group substituted with a halogen atom or an electron-withdrawing group.

R ₁ , R ₂ and R ₃ in the above general formula [I]
At least one of them is preferably a group substituted with a halogen atom or a halogen atom, and particularly preferably a fluorine atom or a fluorinated alkyl group (for example, a monofluoromethyl group, a trifluoromethyl group).

The yellow coupler represented by the general formula [I] is preferably a compound represented by the following general formula [III].

[0029]

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[0030] R ₁ in the general formula [III], R _2, and R ₃ are R _1, R ₂ in the general formula [I], and R
Represents a group synonymous with ₃ . However, in the above general formula [III], at least one of R ₁ , R ₂ , and R ₃ is a halogen atom, an electron-withdrawing group, or a group substituted with a halogen atom or an electron-withdrawing group.

The group represented by R ₇ in the above general formula [III] represents a substitutable group on the benzene ring. For example, the alkyl represented by R ₁ , R ₂ and R ₃ in the above general formula [I]. Group, aryl group, heterocyclic group, halogen atom, electron-withdrawing group, and alkyl group, aryl group, heterocyclic group,
Examples of the groups that may be substituted on each group of the electron-withdrawing group include the same groups. k represents an integer from 0 to 5,
When k is plural, R _7's may be the same as or different from each other, or may be bonded to each other to form a cyclic structure.

In the above general formula [III], Y represents a group which can be substituted on the benzene ring, for example, an alkoxy group, a halogen atom and a dialkylamino group are preferable, and an alkoxy group and a chlorine atom are particularly preferable.

In the above general formula [III], W represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a developing agent. Examples of the group capable of splitting off upon coupling with the oxidized product of the developing agent represented by W in the above general formula [III] include, for example, phenoxy group, alkoxy group,
Examples thereof include an acyloxy group, a carbamoyl group, a sulfonyl group, and a nitrogen-containing heterocyclic group (for example, an imidazolyl group, a pyrazolyl group, a hydantoinyl group, etc.). The group represented by W and capable of splitting off upon coupling with the oxidized product of the developing agent may have a substituent, and examples of the substituent include R ₁ , R ₂ and R ₃ in the above general formula [I]. Represented by an alkyl group, a cycloalkyl group,
Examples thereof include a group having the same meaning as the group described as the substituent of the aryl group, the heterocyclic group and the electron-withdrawing group.

The group represented by W in the above general formula [III] and capable of splitting off upon coupling with the oxidized product of the developing agent is represented by the following general formulas [X], [XI], [XII] and [XII].
I], [XIV], [XV], [XVI], [XVII], [XVII
The groups represented by I], [XIX], and [XX] are preferable.

[0035]

[Chemical 6]

In the above general formula [X], R ₁₀ represents a substitutable group on the benzene ring, for example, the above general formula [I]
In R ₁ , R ₂ , and R ₃ include a group having the same meaning as an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom and an electron-withdrawing group, or a substituent of these groups. The groups having the same meanings as the existing groups can be mentioned. p represents an integer from 0 to 5. When p is plural, R ₁₀ may be different or the same.

In the above general formula [XI], R ₁₁ and R ₁₂
Represents a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group. Examples of the alkyl group, cycloalkyl group, and aryl group represented by R ₁₁ and R ₁₂ include the alkyl group, cycloalkyl group, and aryl group represented by R ₁ , R ₂ , and R ₃ in the above formula [I]. , And a group having the same meaning as the heterocyclic group. These R
_The alkyl group, cycloalkyl group, and aryl group represented by ₁₁ and R ₁₂ may further have a substituent, and examples of the substituent include R ₁ , R ₂ , and R ₃ in the general formula [I]. The alkyl group, the cycloalkyl group, the aryl group, and the group represented by the substituents of the heterocyclic group can be the same as those of the group.
q represents an integer of 1 to 4. EWG represents an electron-withdrawing group, and examples of the electron-withdrawing group include oxycarbonyl group, oxysulfonyl group, carbonyl group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonylamino group, nitro group, cyano group, or halogen. An atom etc. are mentioned.

The above general formulas [XII], [XIII], and [X
IV], R ₁₃ represents an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group, cycloalkyl group, and aryl group represented by R ₁₃ have the same meanings as the alkyl group, cycloalkyl group, and aryl group represented by R ₁ , R ₂ , and R ₃ in the formula [I]. Groups. The alkyl group, cycloalkyl group and aryl group represented by R ₁₃ may further have a substituent, and examples of the substituent include those represented by R ₁ , R ₂ and R ₃ in the general formula [I]. Alkyl group, cycloalkyl group, aryl group,
Examples thereof include a heterocyclic group and a group having the same meaning as the group described as the substituent of the electron-withdrawing group.

The above general formulas [XV], [XVI], [XVII],
In [XVIII] and [XIX], R ₁₄ , R ₁₅ and R ₁₆ each represent a substitutable group on the azole ring, and for example, R ₁ , R ₂ and R ₃ in the general formula [I] are Represented alkyl group, cycloalkyl group, aryl group,
Examples thereof include a heterocyclic group and a group having the same meaning as the group described as the substituent of the electron-withdrawing group.

In the above general formula [XVIII], R ₁₇ is, for example, an alkyl group, a cycloalkyl group, an aryl group represented by R ₁ , R ₂ and R ₃ in the above general formula [I],
And a group having the same meaning as the heterocyclic group, a carbonyl group, a sulfonyl group and the like.

In the above general formulas [XVII] and [XVIII], Z ₁₀ is> N—R ₁₈ (R ₁₈ represents a hydrogen atom, an alkyl group, a cycloalkyl group and an aryl group), —O
-, and -S (O) j _- represents the (j is an integer from 0 to 2).

In the above general formula [XX], Y ₁₀ and Y ₁₁
Is> N—R ₁₈ (R ₁₈ is the above general formula [XVII] and [XVII
A hetero atom or a hetero atom group represented by R ₁₈ in I], -O-, and -S (O) v- (v represents an integer of 0 to 2), or> C =
O,> C (R ₁₉ ) (R ₂₀ ) (R ₁₉ and R ₂₀ are a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group represented by R ₁ , R ₂ and R ₃ in the formula [I]. And a carbon atom group represented by ═C (R ₁₉ ) — and the like. Y ₁₀ and Y ₁₁ may be the same or different.

In the above general formula [XX], Z ₁₁ is -Y ₁₀ -N
-Y ₁₁ - 5 not in cooperation with the to represent a non-metallic atomic group necessary for forming a 6-membered ring. Here, examples of the atomic group necessary for forming the non-metal atom group include, for example, substituted and unsubstituted methylene and methine,>C═O,> N—R ₅ (R ₅ is a hydrogen atom, an alkyl group, a cyclohexyl group). An alkyl group, an aryl group, or a heterocyclic group), -N =, -O-, and -S (O) g- (g represents an integer of 0 to 2) and the like.

The yellow coupler represented by the above general formula [I] may be bonded at any substituent to form a bis form, tris form, tetrakis form or polymer form.

Next, typical specific examples of the yellow coupler represented by the general formula [I] used in the present invention will be shown by using the following general formula [XXI].

[0046]

[Chemical 7]

Examples of the substituent R _A are shown below.

[0048]

Embedded image

Examples of the substituent R _B are shown below.

[0050]

[Chemical 9]

Examples of the substituent R _C are shown below.

[0052]

[Chemical 10]

Examples of the leaving group W are shown below.

[0054]

[Chemical 11]

The typical examples of the yellow coupler represented by the general formula [XXI] used in the present invention are shown below, but the present invention is not limited thereto.

[0056]

[Chemical 12]

The yellow coupler represented by formula (III) of the present invention can be easily synthesized by a conventionally known method. The representative synthetic examples of the present invention are shown below.

Synthesis Example: Synthesis of Exemplified Coupler (15)

[0059]

[Chemical 13]

9.6 g of intermediate A synthesized by the method described in European Patent 598436 was dissolved in 100 ml of chloroform, and 2.9 g of sulfuryl chloride was added dropwise with stirring under ice cooling. After dropping
After stirring at room temperature for 1 hour, the reaction solution was washed twice with 100 ml of water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue obtained was dissolved in 100 ml of acetone and added with N
-4.6 g of benzylhydantoin and 3.3 g of potassium carbonate were added, and the mixture was heated under reflux for 2 hours. After the insoluble material was filtered off, the solvent was distilled off under reduced pressure. 100 ml of ethyl acetate was added to the obtained oily component.
Is added twice with 100 ml of 5% aqueous potassium carbonate solution, and diluted hydrochloric acid 1
Washed twice with 00 ml. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the desired exemplary coupler (15).
6.6 g was obtained. The structure was confirmed by ¹ H NMR spectrum, IR spectrum and mass spectrum.

R ₄ , R ₅ and R in the above general formula [II]
_The substituent represented by ₆ is R in the above formula [I].
_1, R ₂ and the alkyl group mentioned in R _3, R ₁ in the aryl group and heterocyclic group as defined group, and the general formula [I],
Examples thereof include groups which may be substituted on the alkyl group, aryl group and heterocyclic group mentioned for R ₂ and R ₃ , and l, m and n each represent an integer of 0 or 1.

R ₄ , R ₅ and R in the above general formula [II]
_The substituent represented by ₆ is preferably an alkyl group having 6 to 12 carbon atoms, and 0 is preferable as the integer represented by 1, m and n.

R ₄ , R ₅ and R in the above general formula [II]
_{As the} substituent represented by ₆ , R ₄ , R ₅ and R ₆ are preferably octyl groups at the same time.

Specific examples of the high boiling point organic solvent represented by the general formula [II] of the present invention are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

[Chemical 15]

[0067]

Embedded image

[0068]

[Chemical 17]

As the silver halide emulsion used in the present invention, a surface latent image type silver halide emulsion forming a latent image on the surface by imagewise exposure is used, and silver halide forming a negative image by development. An emulsion may be used. or,
Using an internal latent image type silver halide emulsion in which the grain surface is not fogged in advance, image exposure is subjected to fog treatment (nucleation treatment) and then surface development, or after image exposure, while performing fog treatment, the surface The thing which can obtain a positive directly by developing is also used preferably.

The above-mentioned fog treatment may be carried out by exposing the whole surface, chemically using a fog agent, using a strong developing solution, or by heat treatment. The emulsion containing the internal latent image type silver halide emulsion grains is a silver halide grain having a photosensitive nucleus mainly inside the silver halide crystal grains and forming a latent image inside the grains by exposure. The emulsion contained.

Various techniques have been known so far in the technical field of the internal latent image type direct positive. For example, U.S. Patents 2,592,250, 2,466,957, 2,497,875,
2,588,982, 3,761,266, 3,761,276, 3,7
The methods described in 96,577 and British Patent 1,151,363 are known.

Although the mechanism of forming a positive image is not always clear, for example, Photographic Science and Engineering (Photographic Science and Engineering)
and Engineering) Vol. 20, p. 158 (1976), it is described as follows.

The photoelectrons generated in the silver halide crystal grains by imagewise exposure are selectively captured inside the grains to form an internal latent image. Since this internal latent image acts as an effective trap center for electrons in the conduction band, in the exposed particles, the electrons injected in the subsequent fog development process are trapped inside and assist the latent image. Become. In this case, the latent image is inside and therefore not developed by surface development. On the other hand, in particles that have not been subjected to image exposure, at least some of the injected electrons are captured on the surface of the particle and a latent image is formed there, so that the particle is developed by surface development.

The non-pre-fogged internal latent image type silver halide grains which can be used in the present invention form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains. An emulsion having silver halide grains, comprising any silver halide such as silver bromide, silver chloride,
It includes silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like.

Particularly preferably, the coated silver amount is about 1 to 3.5 g.
A portion of the sample coated on the transparent support so as to be in the range of 1 / m ² is exposed to the light intensity scale for a predetermined time from about 0.1 second to about 1 second, and is substantially halogenated. When only the surface image of a grain not containing a silver solvent is developed using the following surface developer A at 4 ° C. for 4 minutes, another part of the same emulsion sample is similarly exposed and It is an emulsion showing a maximum density which is not larger than ⅕ of the maximum density obtained when the image is developed with the following internal developer B at 20 ° C. for 4 minutes. More preferably, the maximum density obtained with surface developer A is no greater than 1/10 of the maximum density obtained with internal developer B.

(Surface developer A) Metol 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 ml (internal developer) Metol 2.0 g Sodium sulfite (anhydrous) ) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water was added to 1000 ml Further, the internal latent image type silver halide emulsions preferably used in the present invention are various. Those prepared by the method are included. For example, conversion type silver halide emulsions described in U.S. Pat.No. 2,592,250, or U.S. Pat.
Nos. 6,3,317,322 and 3,367,778, and silver halide emulsions having internally chemically sensitized silver halide grains, or U.S. Patents 3,271,157 and 3,447,927.
Emulsion having silver halide grains containing a polyvalent metal ion described in U.S. Pat. Or a silver halide emulsion comprising grains having a laminated structure described in JP-A Nos. 50-8524, 50-38525 and 53-2408, and others. Examples thereof include silver halide emulsions described in JP-A-156614 and JP-A-55-127549.

The internal latent image type silver halide grains preferably used in the present invention are silver halides having any halogen composition, such as silver bromide, silver chloride, silver chlorobromide, silver chloroiodide and silver iodobromide. Any silver chloroiodobromide may be used. The grains containing silver chloride have excellent developability and are suitable for rapid processing.

The shape of the silver halide grains used in the present invention is cubic, octahedral, or a mixture of (100) and (111) faces.
It may be a tetrahedron, a shape having a (110) plane, a spherical shape, a flat shape, or the like. An average particle size of 0.05 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having uniform grain size and crystal habit, or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having uniform grain size and crystal habit. Is preferred. In the present invention, the monodisperse silver halide emulsion means that the weight of silver halide contained within a grain size range of ± 20% centered on the average grain size r is
It means 60% or more of the total weight of silver halide grains,
It is preferably 70% or more, more preferably
80% or more. Here, the average particle diameter r is defined as the particle diameter r _i of when the product n _i × r _i ³ of the frequency n _i and r _i ³ of particles having a particle size r _i becomes maximum. (Three significant digits and the least significant digit are rounded off to the nearest four.) The grain size as used herein means the diameter of spherical silver halide grains, and the grain size of other than spherical grains. It is the diameter when the projected image is converted into a circular image of the same area. The particle size is, for example, 1 with an electron microscope.
It can be obtained by enlarging the image by 10,000 to 50,000 times and measuring the particle diameter on the print or the area at the time of projection. (It is assumed that the number of measured grains is 1000 or more indiscriminately.) A particularly preferable highly monodisperse emulsion is (grain size standard deviation / average grain size) × 100 = distribution defined by breadth (%) of distribution. Is less than 20% wide. Here, the average particle size and the particle size standard deviation are obtained from r _i defined above.

The monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed grains at pH and pH.
Under the control of the double jet method. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied.

The fog processing in the internal latent image type direct positive image formation preferably used in the present invention can be carried out by exposing the whole surface or by using a compound which generates fog nuclei, that is, a fog agent.

The entire surface exposure is carried out by immersing the imagewise exposed light-sensitive material in a developing solution or other aqueous solution or moistening it and then uniformly exposing the whole surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the photographic light-sensitive material,
Further, high illuminance light such as flash light may be applied for a short time, or weak light may be applied for a long time. Further, the time of the whole surface exposure can be varied over a wide range so that the best positive image can be finally obtained depending on the photographic light-sensitive material, the development processing conditions, the kind of the light source used and the like. Further, it is most preferable that the exposure amount of the whole surface exposure gives a certain range of exposure amount in combination with the photosensitive material. Usually, when the exposure amount is excessively increased, the minimum density is increased or desensitized, and the image quality tends to be deteriorated.

Next, the fog agent preferably used in the present invention will be described.

A wide variety of compounds can be used as the fog agent used in the present invention, and the fog agent only needs to be present during the development processing. For example, in the constituent layers other than the support of the photographic light-sensitive material (among them, among them). In particular, it is preferably in a silver halide emulsion layer), or in a developing solution or a processing solution prior to the development processing. The amount used can be varied over a wide range depending on the purpose, and the preferable amount added is that when it is added to the silver halide emulsion layer,
1-1,500 mg, preferably 10 per mol of silver halide
~ 1,000 mg. When it is added to a processing solution such as a developing solution, the addition amount is preferably 0.01 to 5 g / liter, particularly preferably 0.05 to 1 g / liter.

Examples of the fogging agent used in the present invention include hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982, or hydrazides or hydrazine compounds described in US Pat. No. 3,227,552; US Pat.
615, 3,718,479, 3,719,494, 3,734,738 and 3,759,901 and heterocyclic quaternary nitrogen salt compounds; further silver halides such as acylhydrazinophenylthioureas described in U.S. Pat. No. 4,030,925. Examples thereof include compounds having an adsorption group on the surface. Further, these fogging agents can be used in combination. For example, RD mentioned above
15162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, or they can be used in combination. Specific examples of useful fogging agents include hydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-acetyl-2-phenylhydrazine, 1-formyl-2- (4-methylphenyl) hydrazine, 1-
Hydrazine compounds such as methylsulfonyl-2-phenylhydrazine, 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine, 1-benzoyl-2-phenylhydrazine and formaldehydephenylhydrazine;
3- (2-formylethyl) -2-methylbenzothiazolium bromide, 3- (2-acetylethyl) -2-benzyl-5-phenylbenzoxazolium bromide, 3- (2-acetylethyl) -2 -Benzylbenzoselenazolium bromide, 2-
Methyl-3- [3- (phenylhydrazino) propyl] benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] benzothiazolium bromide, 1,2
-Dihydro-3-methyl-4-phenylpyrido [2,1-b] benzoselenazolium bromide, 4,4'-ethylenebis (1,2-dihydro-3-methylpyrido [2,1-b] benzothiazo N-substituted quaternary cycloammonium salt such as (b) bromide; 5- (3
-Ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] rhodamine, 1,3-bis [4- (2-
Formylhydrazino) phenyl] thiourea, 7- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate, 1-formyl- 2- 〔4- {3- (2-
Methoxyphenyl) ureido} phenyl] hydrazine and the like.

The photographic light-sensitive material having a silver halide emulsion layer according to the present invention forms a positive image directly by imagewise exposure followed by overall exposure or development in the presence of a fogging agent.

Examples of the developer that can be used in the developer used for developing the photographic light-sensitive material according to the present invention are:
Conventional silver halide developers, for example, polyhydroxybenzenes such as hydroquinone, aminophenols, 3-
Pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or mixtures thereof are included. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N -(β-Methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline Etc. It is also possible to incorporate these developers in the emulsion in advance so that they act on the silver halide during the immersion in the high pH aqueous solution.

The developer used in the present invention may further contain a specific antifoggant and development inhibitor, or these developer additives may be optionally incorporated in the constituent layers of the photographic light-sensitive material. Is also possible.

In the silver halide photographic light-sensitive material of the present invention, known photographic additives can be used.

Known photographic additives include, for example, the compounds described below in RD17643 and RD18716.

Additives RD17643 RD18716 Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right sensitizing dye 23 IV 648 Upper right development accelerator 29 XXI 648 Upper right antifoggant 24 VI 649 Lower right stabilizer Stabilization 〃 Color contamination prevention Agent 25 VII 650 Left-right Image stabilizer 25 VII UV absorber 25-26 VII 649 Right-650 left Filter dye 〃 〃 Whitening agent 24 V Hardening agent 26 X 651 Right Coating aid 26-27 XI 650 Right interface Activator 26-27 XI 650 Right Plasticizer 27 XII 650 Right Sliding agent 〃 〃 Static inhibitor 〃 〃 Matting agent 28 XVI 650 Right binder 29 IX 651 Right In the emulsion layer of the light-sensitive material of the present invention, a color developing agent is used. It is possible to use a dye-forming coupler which forms a dye by a coupling reaction with the oxidant. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, the silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

[0092]

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

Example 1 A polyethylene support was laminated on one side of a paper support, and a polyethylene having 15% by weight of titanium oxide in the binder was laminated on the other side of the first support. Each layer having the constitution shown in (1) was applied to prepare a multilayer color photographic light-sensitive material sample 1-1.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate and potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.
A 30 μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.42 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Emulsion EM-2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate and potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.
An 18 μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.25 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-2. The breadth of distribution of this emulsion EM-2 was 8%.

(Preparation of Blue-Sensitive Emulsion EM-B) After sensitizing sensitizing dye D-1 to EM-1, 600 mg of T-1 / 1 mol of silver was added to obtain blue-sensitive emulsion EM-B. It was made.

(Preparation of Green Sensitive Emulsion EM-G) A green sensitive emulsion EM-G was prepared in the same manner as the blue sensitive emulsion except that the sensitizing dye D-2 was added to EM-2 for color sensitization.

(Preparation of red-sensitive emulsion EM-R) Red-sensitive emulsion EM-R was prepared in the same manner as blue-sensitive emulsion except that sensitizing dyes D-3 and D-4 were added to EM-2 for color sensitization. It was made.

(Preparation of pan-sensitive emulsion EM-P) Same as the blue-sensitive emulsion except that sensitizing dyes D-1, D-2, D-3 and D-4 were added to EM-1 for color sensitization. Pan-sensitive emulsion EM-
P was prepared.

T-1: 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene

[0103]

Embedded image

EM-B, EM-G, EM-R, EM
-A color photographic light-sensitive material having the following constitution using P-
1 was produced. The first layer to the eighth layer were coated on the surface of the above-mentioned support in the following constitution, and the ninth layer was coated on the back surface side. still,
Sample 1 was prepared using SA-1 and SA-2 as coating aids and H-1 and H-2 as hardeners.
The amount of silver applied was a value calculated in terms of silver.

SA-1: sulfosuccinic acid di (2-ethylhexyl) ester sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester Sodium H-1: 2,4-dichloro-6-hydroxy-s-triazine
Sodium H-2: Tetrakis (vinylsulfonylmethyl) methane layer composition Coating amount (g / m ² ) Eighth layer gelatin 0.78 (UV absorbing layer) UV absorber (UV-1) 0.065 UV absorber (UV-2 ) 0.120 UV absorber (UV-3) 0.160 Solvent (SO-2) 0.1 Silica matting agent 0.03 7th layer Gelatin 1.14 (Blue sensitive layer) Blue sensitive emulsion EM-B (Coating silver amount) 0.40 Yellow coupler (YC-1) ) 0.656 Anti-stain agent (AS-2) 0.02 Solvent (SO-1) 0.072 Inhibitor (ST-1, ST-2, T-1) Sixth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1, 0.055 Solvent (SO-2) 0.072 Fifth layer Gelatin 0.42 (Yellow yellow colloidal silver 0.1 colloidal silver layer) Color mixing inhibitor (AS-1, 3, 4, 5, 6 equivalents) ) 0.04 Solvent (SO-2) 0.049 Polyvinyl ester Loridone (PVP) 0.047 Anti-irradiation dye (AI-3) 0.03 4th layer Gelatin 0.54 (Intermediate layer) Color mixture inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.14 (Green-sensitive layer) Green-sensitive emulsion EM-G (Amount of coated silver) 0.50 Magenta coupler (MC-1) 0.20 Yellow coupler (YC-2) 0.06 Anti-staining agent (AS-2) 0.019 Solvent (SO) -1) 0.31 Inhibitor (ST-1, ST-2, T-1) Second layer Gelatin 0.75 (Intermediate layer) Color mixture inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO -2) 0.072 Anti-irradiation dye (AI-1) 0.01 Anti-irradiation dye (AI-2) 0.01 First layer Gelatin 1.38 (Red-sensitive layer) Red-sensitive emulsion EM-R (coated silver amount) 0.36 Cyan coupler (CC) -2) 0.44 solvent (SO-1) 0.31 Inhibitor (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-1) Ninth layer Gelatin 6.00 (Back layer) Silica matting agent 0.65 SO-1: Dibutylphthalate SO-2: Dioctylphthalate AS -1: 2,4-di-t-octylhydroquinone AS-2: 2,4-di-t-butylhydroquinone ST-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-2: N- Benzyladenine

[0106]

[Chemical 19]

[0107]

Embedded image

[0108]

[Chemical 21]

[0109]

[Chemical formula 22]

Next, Sample 1-2 was prepared in the same manner as Sample 1-1 obtained as described above except that the yellow coupler of the seventh layer was replaced with the yellow coupler of the present invention shown in Table 1.
1-10 was created.

Samples 1-1 to 1-10 thus obtained were exposed under the exposure condition -1 shown below by contacting a black plate and a cyan plate among halftone originals. Then, the black plate and the magenta plate were brought into close contact with each other and exposed under the exposure condition-2 shown below. Further, the black plate and the yellow plate were brought into close contact with the sample and exposed under the exposure condition-3 shown below.

(Exposure condition-1) When exposing each light-sensitive material to white light through a red filter (Ratten No. 26) and an ND filter, the ND filter density is adjusted so that the red light density after the development processing is minimized. Exposure for 0.5 seconds with the minimum exposure amount.

(Exposure condition-2) When exposing each light-sensitive material to white light through a green filter (Ratten No.58) and an ND filter, the ND filter density is adjusted so that the green light density after development is minimized. Exposure for 0.5 seconds with the minimum exposure amount.

(Exposure condition-3) When exposing each light-sensitive material to a white light through a blue filter (Ratten No. 47B) and an ND filter, the ND filter density is adjusted so that the blue light density after the development processing becomes the minimum. Exposure for 0.5 seconds with the minimum exposure amount.

The exposure conditions (exposure conditions-1 to 3)
A daylight fluorescent lamp was used as the light source.

The exposed sample was treated under the following processing conditions-
An image was obtained by performing the processing according to 1. The conditions of the development processing and the prescription of the processing liquid are as follows.

(Processing Conditions-1) Processing Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds (1 lux) Development 37 ° C 95 seconds Bleach-fixing 35 ° C 45 seconds Stabilization 25-30 90 seconds dry 60-85 degrees 40 seconds-Processing solution composition- (Color developer) 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-1 0.1g Hydroxylamine sulfate 5.0g Diethylenetriamine sodium pentaacetate 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) 4.5g Aniline sulfate Optical brightener (4,4'-diamino Stilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 15.0 ml Add water to bring the total volume to 1 liter and adjust the pH to 10.15.

(Bleaching Fixing Solution) Diethylenetriaminepentaacetic acid ferric ammonium 90.0 g Diethylenetriaminepentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution)
180 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 1 liter.

(Stabilizing solution) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Water Ammonium oxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide or Adjust the pH to 7.5 with sulfuric acid. The stabilization process is 2
A counter-current system with a tank configuration was adopted.

After the treatment, the obtained image was measured, and the results obtained from the characteristic curve of the yellow color image and the solid image portion of the yellow color image were visually evaluated for the degree of approximation to the printing ink sample. The results are shown in Table 1.

[0121]

[Table 1]

A Very close to image obtained with printing ink B Similar to image obtained with printing ink C Intermediate between B and D D Difficult to use as a color proof. It can be seen that the sample obtained from the coupler and the high-boiling-point organic solvent has an extremely excellent color tone for color proofing, and the white background is also extremely excellent like the color tone.

Example 2 Samples 1-1 to 1-16 prepared in Example 1 were replenished in the developing solution in processing step-1 during continuous processing after exposure under the exposure conditions-1, 2 and 3 described above. Continuous processing was carried out until the total amount of the replenisher became three times that of the developing solution layer, and processing was carried out using the developing solution, the bleach-fixing solution and the stabilizing solution obtained after the continuous processing.

The formula of the replenisher for running is shown below.

(Color development replenisher) benzyl alcohol 18.5 ml cerium sulphate 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) 5.4 g Aniline sulfate Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Add water to make the total volume 1 liter and adjust to pH 10.35.

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

(Stabilizer Replenisher) Same as the above stabilizer.

The replenishing amount was 320 ml / m ² for both the developing solution, the bleach-fixing solution and the stabilizing solution.

After the treatment, the obtained image was measured, and the results obtained from the characteristic curve of the yellow color image and the solid image part of the yellow color image were visually evaluated for the degree of approximation to the printing ink sample. The results are shown in Table 2.

[0130]

[Table 2]

A Very close to image obtained from printing ink B Similar to image obtained from printing ink C Intermediate between B and D D It is difficult to use as a color proof. It can be seen that also in the sample obtained from the yellow coupler of the present invention and the high boiling point organic solvent treated with the treatment liquid, the white background as well as the color tone is extremely excellent for color proofing.

Example 3 Samples 1-1 to 1-16 prepared in Example 1 were used at room temperature 50
After keeping it at 80 ℃ and humidity of 80% for 15 days in a dark room,
After the exposure under the exposure conditions-1, 2 and 3, the processing step-1
In the developer, the resulting image was measured, the results obtained from the characteristic curve of the yellow color image, and the solid image part of the yellow color image were subjected to a visual sensory evaluation of the degree of approximation to the printing ink sample. The results are shown in Table 3 which was compared with the results obtained in Example 1.

[0133]

[Table 3]

A Very close to the image obtained from the printing ink B Near to the image obtained from the printing ink C Intermediate between B and D D Difficult to use as a color proof. It can be seen that the sample obtained from the high-boiling organic solvent gives a yellow image having an extremely excellent color tone and white background even after storage with time.

[0135]

According to the present invention, there is provided a color proof light-sensitive material having a color tone similar to that of a printing ink, an extremely excellent white background, and continuous processing compatibility, and further excellent stability of the light-sensitive material over time. be able to.

Claims (3)

[Claims] 1. A halogenation characterized in that an acylacetamide type yellow coupler having a group represented by the following general formula [I] is contained together with a high boiling point organic solvent represented by the following general formula [II]. Silver photographic light-sensitive material. Embedded image Wherein, R _1, R ₂ and R ₃ represents a substituent, at least one halogen atom in the substituent represented by R _1, R ₂ and R _3, an electron-withdrawing group or a halogen atom, It represents a group in which an electron-withdrawing group is substituted. ] [Chemical 2] [In the formula, R ₄ , R ₅ and R ₆ represent a substituent, and l, m and n represent an integer of 0 or 1. ] 2. At least one of the substituents represented by R ₁ , R ₂ and R ₃ in the general formula [I] is a halogen atom or a group substituted with a halogen atom. 1. The silver halide photographic light-sensitive material as described in 1. 3. A yellow image, a magenta image, which is exposed and processed based on halftone dot image information consisting of color-separated yellow image information, magenta image information, cyan image information and black image information. A color proof is created by forming a cyan image.
Or the silver halide photographic light-sensitive material described in 2.