JPH0743869A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE:To improve the deterioration of dot reproduction performance due to development processing conditions, running processing, and raw stock storage and to obtain stable tone images by incorporating a specified compound in at least one of silver halide emulsion layers. CONSTITUTION:The silver halide color photographic sensitive material comprises a reflective support coated with a polyolefin resin on both sides and a hydrophilic colloidal layer containing a white pigment and silver halide emulsion layers on one side of this support, and contains in at least one of the emulsion layers at least cane kind of compound represented by formula I or II in which each of R1 and R2 is H or <=5C alkyl; n is an integer of 1-3; and each of R11-R16 is, independently, H, halogen, sulfo, carboxy, cyano, alkyl, or the like; and each of R17 and R18 is, independently, H, alkyl, aryl, or a heterocyclic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, in particular, a color image for proofing (color proof) from a plurality of black and white halftone dots 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 which can be preferably used for producing the above and a method for producing a color proof using the same.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials (hereinafter abbreviated as color light-sensitive materials) are usually subjected to color reproduction by a subtractive color method, and after imagewise exposure, they are exposed with a color developing solution. Color images are obtained by developing silver particles, reacting the produced oxidation product of a color developing agent with a yellow, magenta and cyan dye forming coupler, followed by bleach-fixing treatment and washing or stabilizing treatment. Improvement of image quality is important for color images obtained in this way.

The color reproducibility of a color light-sensitive material depends on various factors. For example, the spectral sensitivity distribution of each light-sensitive emulsion layer, the spectral absorption characteristics of each dye image produced, the degree of color mixing between each dye image, etc. This is a factor affecting reproducibility.

Although the color reproducibility is improved by sharpening the spectral absorption characteristics of the dye image forming the image, on the other hand, when the spectral distribution characteristics of the viewing light source are changed, the colors look different and the shadow portion appears. There is a drawback that the image is not reproduced sufficiently black and the image has no blackness.

As a technique for improving the tightness of a black background, for example, JP-A-53-133432 and JP-A-55-59462 disclose an attempt to improve the reproducibility of a black background by using a color photographic light-sensitive material provided with a black image forming layer. Techniques for doing so are disclosed. According to this method, the black reproducibility is improved, but the sharpness is deteriorated, and it has been found that there are drawbacks such that the black reproducibility of fine lines such as black characters is not sufficient.

[0006] In addition, as a technique for improving sharpness, a technique using an anti-irradiation dye and a technique using black colloidal silver are disclosed, but they are accompanied by a significant loss of sensitivity and a white background after treatment. There is a problem such as contamination remaining. For the purpose of preventing the deterioration of the sharpness of the reflective support, the filling rate of the white pigment in the resin coating layer of the base paper is increased, or a photosensitive material having a hydrophilic colloid layer containing the white pigment is disclosed in, for example, JP-A-54 -46035, JP-A-2-28640,
As disclosed in Japanese Examined Patent Publication No. 2-29203, Japanese Examined Patent Publication No. 59-820, and Japanese Unexamined Patent Publication No. 3-89340, the gradation of the legs changes when the replenishment amount is small and the processing conditions such as fatigue of the developer change. It was also found that there is a problem that the color tone of the highlight part changes.

On the other hand, 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 in the conventional color plate-making / printing process, a photopolymer or a diazo compound is used. 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.

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

Further, after transferring to a support using a photosensitive coloring sheet and forming an image by exposure and development, another coloring sheet is laminated thereon, and the same process is repeated to obtain a color proof. How to create is
It is known from 47-27441 and JP-A-56-501217.

Further, there is disclosed a method of forming each color image obtained by exposing and developing the corresponding color separation film using a photosensitive color sheet and transferring the color image on one support.
Known as No. 59-97140. 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, the operation is time-consuming, and the manufacturing cost is high.

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-56-104335. 62-280746, 62-280747, 62-
280748, 62-280749, 62-280750, 62-28084
No. 9 etc.

In this method, a color-separated black-and-white halftone image composed of a plurality of sheets converted from a color original into color-separated halftone images is successively printed on one sheet of color paper by a method such as contact printing to develop the color. A color image formed by a dye formed from a coupler imagewise by color development after development is used as a proof image.

However, this technique has a drawback that the reproducibility of the halftone dots is likely to vary, especially in an image area having a small halftone dot area. In particular, when the development processing conditions vary, the variation is large, and the improvement is improved. Is requested.

In addition, the above-mentioned Japanese Patent Publication No. 2-29203 and Japanese Patent Publication No. 59-820.
When the light-sensitive material having the hydrophilic colloid layer containing the white pigment described in 1) is simply applied to a color proof light-sensitive material, further reproducibility of small dots in a region having a small halftone dot area by running processing and raw sample storage. Was found to deteriorate.

[0017]

In contrast to the above problems, the object of the present invention is to provide halftone image information obtained by color separation and halftone image conversion using a silver halide color photographic light-sensitive material. And a silver halide color photographic light-sensitive material for a color proof, in which deterioration of dot reproducibility due to development processing conditions, running processing, and raw sample storage is improved when a color proof is produced from It is to provide a method for producing a color proof using.

[0018]

The above object of the present invention is to provide a hydrophilic colloid layer containing a white pigment on one side of a reflective support having a polyolefin resin coating layer on both sides of the support and a halogenated layer. In a silver halide color photographic light-sensitive material having a silver emulsion layer, at least one of the silver halide emulsion layers contains at least a compound represented by the general formula [1] (Chemical formula 1) or [2] (Chemical formula 2). A silver halide color photographic light-sensitive material characterized by containing one kind and an image-forming method characterized by obtaining an image by exposing the photographic light-sensitive material two or more times.

The present invention will be described below.

The white pigment used in the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina,
Zirconium oxide, kaolin and the like can be used, but titanium dioxide is preferable among them for various reasons.
The white pigment is dispersed in a water-soluble binder of a hydrophilic colloid such as gelatin which allows the treatment liquid to penetrate.
The coating amount of the white pigment is preferably 1 g / m ² to 50
in the range of g / m ^2, to more preferably 2 g / m ² to 20
It is in the range of g / m ² .

The hydrophilic colloid layer containing the white pigment according to the present invention is preferably provided between the support and the silver halide emulsion layer closest to the support. Between the support and the silver halide emulsion layer closest to the support, a non-photosensitive hydrophilic layer such as a white pigment-containing layer, an undercoat layer on the support, or an intermediate layer at an optional position may be provided. A colloidal layer can be provided.

The reflection support used in the present invention is preferably made of a base paper, on both sides of which a polyolefin resin is laminated. As the reflective support used in the present invention, a synthetic resin film support such as polypropylene whose surface is coated with a polyolefin resin can also be used. The thickness of the reflective support according to the present invention is not particularly limited, but a thickness of 80 to 160 μm is preferably used.

Next, the general formula [1] used in the present invention,
The compound represented by [2] will be described.

The color light-sensitive material of the present invention contains at least one of these compounds in the silver halide emulsion layer and / or the non-light-sensitive layer.

In the general formula [1] (Formula 1), R ₁ and R ₂
Represents a hydrogen atom or an alkyl group having 5 or less carbon atoms (for example, methyl, ethyl, i-propyl, butyl, t-butyl, pentyl, t-pentyl, neo-pentyl), and n is an integer of 1 to 3.

In the general formula [2] (Chemical formula 2), R _{11 to} R
_The group represented by ₁₆ is independently a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group acylamino group, a sulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, Represents an arylthio group, an acyl group, an acyloxy group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group or a sulfamoyl group, wherein R ₁₁ and R ₁₂ or R
₁₄ and R ₁₅ may together form a carbocycle or a heterocycle, and R _{11 to} R ₁₆ may be substituted with the substituents mentioned above as the substituents.

The above R ₁₇ and R ₁₈ are, for example, methyl, i-
Examples thereof include alkyl groups such as propyl and benzyl, aryl groups such as phenyl and p-tolyl, and heterocyclic groups such as pyridin-2-yl group.

R ₁₇ and R ₁₈ may together form a carbocycle (for example, a cyclohexane ring) or a heterocycle (for example, a tetrahydropyran ring), or may be further substituted with a substituent.

Specific examples of the compounds represented by the general formulas [1] and [2] are shown below, but the compounds are not limited to these.

[0030]

[Chemical 3]

The amount of the compound of the general formula [1] added is 0.
001 to 0.50 g / m ² is preferable, more preferably 0.005 to 0.2
It is 0 g / m ² . The compounds may be used alone or in combination of two or more kinds. Further, a quinone derivative having 5 or more carbon atoms may be added to the compound of the general formula [1] for use. However, in any of these cases, the amount used is preferably in the range of 0.001 to 0.50 g / m ² k as a whole.

[0032]

[Chemical 4]

[0033]

[Chemical 5]

[0034]

[Chemical 6]

The compound of the general formula [2] is disclosed in JP-A-52-14623.
5, it can be synthesized according to the method described in JP-B-56-21145, JP-B-59-37497 and the like. The amount of the compound added is 2 × 10 ⁻⁸ to 2 × 10 ⁻² mol / m ² , preferably 2 × 10 ^−7.
To 2 × 10 ⁻³ mol / m ² , more preferably 2 × 10 ⁻⁶ to 2 × 10
^-4 mol / m ² range.

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. Also, using an internal latent image type silver halide emulsion in which the grain surface has not been previously fogged, fog treatment (nucleation treatment) is performed after image exposure, and then surface development is performed, or after fog treatment is performed after image exposure. Those which can directly obtain a positive image by carrying out surface development can also be preferably used.

The above-mentioned fog treatment may be carried out by exposing the entire 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)
andEngineering), Vol. 20, p. 158 (1976), describes as follows.

Photoelectrons generated in the silver halide crystal grains by the 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 mainly form a latent image 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 1/5 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 less than the maximum density obtained with internal developer B.
It is not larger than 1/10.

(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 The internal latent image type silver halide emulsion preferably used in the present invention is Those prepared by various methods 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) face and (111) face.
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 figures and the least significant figure are rounded off to the nearest four.) The grain size referred to here is the diameter in the case of spherical silver halide grains, and the grain size in the case of grains other than spherical. 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.
This can be obtained by enlarging the image from 10,000 times to 50,000 times, and measuring the particle diameter on the print or the area at the time of projection. (The number of measured grains is indiscriminately 1000 or more.) A particularly preferable highly monodisperse emulsion is (grain size standard deviation / mean 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 can be obtained by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed grains by the double jet method under the control of pAg and pH. 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.

In the silver halide color photographic light-sensitive material of the present invention, the yellow image forming silver halide emulsion layer, the magenta image forming silver halide emulsion layer and the cyan image forming silver halide emulsion layer have mutually different spectral sensitivities. It can have a wavelength range. The spectral sensitivity wavelength regions may be different from each other and may be any wavelength region from the visible region to the infrared region and can be arbitrarily selected.

In the present invention, the yellow image forming layer, the magenta image forming layer and the cyan image forming layer have mutually different spectral sensitivities. This is at least 4 more than the spectral sensitivity of other layers at any wavelength in the spectral sensitivity range of each layer.
It is sufficient if there is a wavelength exhibiting a double sensitivity, preferably at least a wavelength exhibiting a sensitivity of 8 times.

In one preferred embodiment, the spectrally sensitized regions of the silver halide emulsion are such that the yellow imaging layer contains a blue sensitive silver halide emulsion and the magenta imaging layer comprises a green sensitive silver halide emulsion layer. In addition, the cyan image forming layer can contain a red sensitive silver halide emulsion.

In this case, the type of color of the formed image,
The color sensitivity of the silver halide emulsion can be taken in any combination.

In one preferred embodiment of the present invention, for example, the yellow image-forming layer contains a blue-sensitive emulsion, the magenta image-forming layer contains a green-sensitive emulsion and the cyan image-forming layer contains a red-sensitive emulsion. It contains an emulsion.

The yellow image forming layer, the magenta image forming layer and the cyan image forming layer of the present invention are laminated and coated on a support, but the order from the support may be any order.

One preferable embodiment is, for example, a cyan image forming layer, a magenta image forming layer from the side closer to the support,
It becomes the yellow image forming layer. In addition to these, an intermediate layer, a filter layer, a protective layer and the like can be arranged as required.

In the present invention, the yellow image component, the magenta image component and the cyan image component are formed based on the halftone dot image information consisting of the color-separated yellow image information, magenta image information, cyan image information and black image information. As described above, it is preferable to expose the silver halide photographic light-sensitive material to form a color proof.

That is, as shown above, a silver halide color photographic light-sensitive material comprising a yellow image-forming silver halide emulsion layer, a magenta image-forming silver halide emulsion layer and a cyan image-forming silver halide emulsion layer is reticulated. It is also possible to perform exposure based on dot image information to form a corresponding halftone dot image.

The silver halide used in the present invention can be optically sensitized by a commonly used sensitizing dye. It is also useful for the silver halide emulsion of the present invention to use a combination of sensitizing dyes used for supersensitization such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion. Regarding the sensitizing dyes, Research Disclosure (hereinafter abbreviated as RD) Nos. 15162 and 17643 can be referred to.

In the silver halide photographic light-sensitive material of the present invention, yellow, magenta and cyan single colors of the yellow image forming layer, the magenta image forming layer and the cyan image forming layer after the photographic processing including the color development processing step are performed. A silver halide color photographic light-sensitive material having a gradation of at least 1.7 is preferable. Here, the foot gradation is represented by the absolute value of the slope of a straight line connecting a point showing the minimum density of 0.15 and a point showing the minimum density of 0.80 in the characteristic curve.

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 entire surface or using a compound which generates fog nuclei, that is, a fogging agent.

The whole 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 at the time of development processing. For example, in the constituent layers other than the support of the photographic light-sensitive material (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 according to the purpose. The preferable addition amount is 1 to 1,500 mg, preferably 10 to 1 mol per mol of silver halide when added to the silver halide emulsion layer. It is 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 / l, particularly preferably 0.05 to 1 g / l.

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.
No. 615, No. 3,718,479, No. 3,719,494, No. 3,734,738 and No. 3,759,901, 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
N-substituted quaternary cycloammonium salts such as -dihydro-3-methylpyrido [2,1-b] benzothiazolium bromide; 5-
(3-Ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] rhodamine, 1,3-bis [4-
(2-Formylhydrazino) phenyl] thiourea, 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-1
0-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 subjecting it to imagewise exposure followed by full 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 immersion in a 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.

Known silver halide photographic additives can be used in the silver halide photographic light-sensitive material of the present invention.

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

Additive 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 staining 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 〃 〃 Antistatic agent 〃 〃 Matting agent 28 XVI 650 Right binder 29 IX 651 Right 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 so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the 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.

These dye-forming couplers preferably have a group called a ballast group having a carbon number of 8 or more, which makes the coupler non-diffusible in the molecule. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two equivalence may be used. Releases a development inhibitor along with development, releases a development inhibitor at the same time as a DIR coupler that improves image sharpness and image graininess, and produces a colorless compound by coupling reaction with an oxidized product of a developing agent. DIR compounds may be used.

The DIR coupler and the DIR compound used have an inhibitor directly bound to the coupling position and an inhibitor bound to the coupling position via a divalent group and are separated by the coupling reaction. Those which are bonded so as to release the inhibitor by intramolecular nucleophilic reaction, intramolecular electron transfer reaction and the like (referred to as timing DIR coupler and timing DIR compound) are included.

Further, a colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with the dye-forming coupler.

Known acylacetanilide type couplers can be preferably used as the yellow dye-forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As the magenta coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers, acylacetonitrile couplers, indazolone couplers and the like can be used.

As the cyan dye-forming coupler, known phenol type, naphthol type or imidazole type couplers can be used.

For example, a phenolic coupler substituted with an alkyl group, an acylamino group, an ureido group or the like,
Typical examples include a naphthol-based coupler formed from a 5-aminonaphthol skeleton and a 2-equivalent naphthol-based coupler having an oxygen atom introduced as a leaving group.

In the magenta image forming layer of the color photographic light-sensitive material of the present invention, it is preferable to use a yellow coupler in combination with a magenta coupler in order to bring it closer to the color tone of the printing ink.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention and / or a processing solution for processing the light-sensitive material.

As the fluorescent whitening agent, stilbene-based, triazine-based, imidazolone-based, pyrazoline-based, triazole-based, coumarin-based, acetylene-based, oxazole-based, and oxadiazole-based fluorescent whitening agents can be preferably used. These optical brighteners are disclosed in US Pat.
2,581,057, 2,618,636, 2,702,296, 2,7
No. 13,054, No. 2,715,630, No. 2,723,197, No. 3,269,84
No. 0, 3,513,102, 3,615,544, 3,615,547,
No. 3,684,729, No. 3,788,854, No. 3,789,012, British Patents 669,590, No. 672,803, No. 712,764, Dutch Patent No. 74,109, German Patent No. 911,368, German Published Publication (OLS) No. 2,525,680, Japanese Patent Publication No. 34-7127. Etc. These compounds may be water-soluble or insoluble and may be used in the form of dispersion.

Examples of the support which can be used in the light-sensitive material of the present invention include RD17643, page 28, and R
Examples include those described on page 647 of D18716. Suitable supports are polymer films, papers, etc., which may be treated for enhancing the adhesiveness, antistatic property and the like.

[0081]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 Polyethylene is provided on one side of a paper support, and titanium oxide is provided on the first layer side of the other side. Each layer having the constitution shown below was coated on a support having a thickness of 110 μm laminated with polyethylene containing the above to prepare a multilayer color photographic light-sensitive material.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, 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 0.30
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so that a cube was obtained as a 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, the 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 0.18
A 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) EM-1
After sensitizing the dye by adding the sensitizing dye D-1, to 600 mg of T-1 was added per mol of silver to prepare a blue-sensitive emulsion EM-B.

(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

[0091]

[Chemical 7]

Using EM-B, EM-G, and EM-R, the first to eighth layers were coated on the surface of the support in the following constitution. SA-1 and SA-2 as coating aids
And using H-1 and H-2 as hardeners, Sample 1-1 was prepared.

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 1.43 (Blue sensitive layer) Blue sensitive emulsion EM-B (Coating silver amount) 0.5 Yellow coupler (YC-1) ) 0.82 Anti-stain agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-1, ST-2, T-1) 6th layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 5th layer gelatin 0.42 (Yellow yellow colloidal silver 0.1 colloidal silver layer) Anti-color mixing agent (AS-1) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 4th layer gelatin 0.54 ( Interlayer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.43 (Green sensitive layer) Green sensitive emulsion EM-G (Coating silver amount) 0.50 Magenta coupler (MC-1) 0.25 Yellow Coupler (YC-2) 0.06 Anti-stain 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) 0.055 Solvent (SO-2) 0.072 First layer Gelatin 1.38 (Red-sensitive layer) Red-sensitive emulsion EM-R (coated silver amount) 0.30 Cyan coupler (CC-1) 0.44 Solvent (SO-1) 0.31 Anti-stain agent (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-1) The coated silver amount is in terms of silver.

Sample 1-2 was prepared in the same manner as Sample 1-1.
Was produced. However, the S-1 layer and the S-2 layer having the following constitution were applied between the support and the first layer.

S-2 Layer Gelatin 0.5 (Intermediate Layer) S-1 Layer Gelatin 1.5 (White Pigment Layer) Anatase type titanium dioxide (W-10; manufactured by Ishihara Sangyo Co., Ltd.) 3.0 For Samples 1-1 and 1-2 above Coating was performed in exactly the same manner except that AS-2 in the first layer, the third layer and the seventh layer was changed to the compounds shown in Table 1 to obtain samples 1-3, 1-4 and 1-5, respectively.

In the same manner as in Sample 1-1, on the support, the EM-B, EM-G, EM-R and EM- were prepared.
A color photographic light-sensitive material-1 using P and having the following constitution
-6 was produced.

Layer composition Coating amount (g / m ² ) 10th layer Gelatin 0.78 (UV absorbing layer) UV absorbing agent (UV-1) 0.065 UV absorbing agent (UV-2) 0.120 UV absorbing agent (UV-3) ) 0.160 Solvent (SO-2) 0.1 Silica matting agent 0.03 9th layer Gelatin 1.43 (blue sensitive layer) Blue sensitive emulsion EM-B (coated silver amount) 0.4 General sensitive emulsion EM-P (coated silver amount) 0.1 Yellow coupler ( YC-1) 0.82 Anti-stain agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-1, ST-2, T-1) Eighth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS -1) 0.055 Solvent (SO-2) 0.072 7th layer Gelatin 0.42 (Yellow yellow colloidal silver 0.03 Colloidal silver layer) Anti-color mixing agent (AS-1) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 6 layers gelatin 0.54 (intermediate layer) Color mixture inhibitor (AS-1) 0.055 Solvent (SO-2) 0.072 Fifth layer Gelatin 1.43 (Green-sensitive layer) Green-sensitive emulsion EM-G (coated silver amount) 0.40 Pan-sensitive emulsion EM-P (coated silver amount) 1.10 Magenta coupler ( MC-1) 0.25 Yellow magenta (YC-1) 0.06 Anti-staining agent (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-1, ST-2, T-1) Fourth layer gelatin 0.75 ( Intermediate layer) Mixed color inhibitor (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.38 (Red sensitive layer) Red sensitive emulsion EM-R (Amount of coated silver) 0.24 General sensitive emulsion EM-P (Coated) Silver amount) 0.06 Cyan coupler (CC-1) 0.44 Solvent (SO-1) 0.31 Anti-staining agent (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-1) Second layer Gelatin 0.5 (Intermediate) Layer) First layer Gelatin (white pigment layer) Anatase type titanium dioxide (W-10 Manufactured by Ishihara Sangyo Co., Ltd.) 3.0 SO-1: trioctyl phosphate SO-2: dioctyl phthalate 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

[0098]

[Chemical 8]

[0099]

[Chemical 9]

Similarly to the above 1-6, the third layer, the fifth layer,
Application was performed in exactly the same manner except that AS-2 in the ninth layer was changed to the compound in Table 1, to obtain Sample 1-7.

[0101]

[Table 1]

Samples 1-1 to 7 obtained as described above
On the other hand, among the original halftone dots, a black plate and a cyan plate were brought into close contact with the sample and exposed under the exposure condition-1 shown below. Next, the black plate and the magenta plate were brought into close contact with the sample 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.

Each of the light-sensitive materials thus exposed was processed by the development processing steps shown below to obtain a dye image consisting of halftone dots.

The results of the obtained concentration measurement are shown. The concentration was measured using PD-65 manufactured by Konica.

(Exposure condition-1) Each light-sensitive material was passed through a red filter (Ratten No. 26) and an ND filter to adjust the ND filter density when exposing white light.
With the minimum exposure amount that minimizes the red light density after development processing
Expose for 0.5 seconds.

(Exposure condition-2) Each photographic material was passed through a green filter (Ratten No. 58) and an ND filter to adjust the ND filter density when white light was exposed.
With the minimum exposure amount that minimizes the green light density after development processing
Expose for 0.5 seconds.

(Exposure condition-3) Each light-sensitive material was passed through a blue filter (Ratten No. 47B) and an ND filter, and when the white light was exposed, the ND filter density was adjusted to minimize the green light density after development. Exposure for 0.5 seconds with the minimum exposure amount.

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

Processing was carried out according to the following processing step-1 (new solution processing). However, the fog exposure was uniformly exposed on the entire surface of the light-sensitive material through the layer of the developing solution having a thickness of 3 mm while being immersed in the developing solution.

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 ° C 90 seconds Dry 60- 85 ° C 40 seconds Processing solution composition (color developer) Benzyl alcohol 15ml Ce ₂ (SO ₄ ) ₃ 0.015g Ethylene glycol 8.0ml Potassium sulfite 2.5g Potassium bromide 0.6g Sodium chloride 0.2g Potassium carbonate 25.0g T-1 0.1g Hydroxylamine sulphate 5.0g Diethylenetriamine 5 sodium acetate 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulphate 4.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium hydroxide 2.0g Diethylene glycol 15.0ml Add water to make the total volume 1 liter and adjust the pH to 10.15.

The results are shown in Table 2.

The small point reproducibility was evaluated by 4 grades by visually observing the reproducibility of 5% halftone dots and the point quality.

⊚: Excellent ○: Good Δ: Practical limit ×: Not practical (1) Evaluation when the developer-stabilizer is a new solution (2) For developer-stabilizer, the total amount of replenisher is the developing tank. Treatment up to 3 times the capacity Evaluation with treatment liquid obtained by running running treatment on Sample 1-4 (3) Sample 1-1 stored under conditions of temperature 50 ° C and 80% RH for 5 days Treated with running liquid

[0114]

[Table 2]

As is clear from the results of Table 2, according to the present invention, it is possible to stably obtain the small point reproducibility, which is one of the most important performances as a color proof.

Example 2 Samples 1-4 of Example 1 were prepared by changing the addition amount of the compound represented by the general formula [1] as shown in Table 3 and exposed in the same manner as in Example 1. , And the same evaluation was performed.

[0117]

[Table 3]

As a result, it was found that, when the amount of the compound represented by the general formula [1] added was outside the amount added in the present invention, the expected effect and the stability of reproducing small dots cannot be sufficiently obtained. .

[0119]

According to the present invention, when a color proof is prepared from halftone image information obtained by color separation and halftone image conversion using a silver halide color photographic light-sensitive material, development processing conditions and running treatment are carried out. , A silver halide color photographic light-sensitive material for a color proof, which can be obtained as an image with a stable color tone in which the deterioration of small dot reproducibility due to the storage of raw samples is improved.
And a method for producing a color proof using the same.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/91 5/08 G03F 3/10 B 7369-2H

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having a hydrophilic colloid layer containing a white pigment and a silver halide emulsion layer on one side of a reflective support having a polyolefin resin coating layer on both sides of the support. A silver halide color photographic light-sensitive material characterized in that at least one of the silver halide emulsion layers contains at least one compound represented by the following general formulas [1] and [2]. [Chemical 1] [In the formula, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 5 or less carbon atoms, and n represents an integer of 1 to 3. ] [Chemical 2] [In the formula, R _{11 to} R ₁₆ are each independently a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group, an acyl group, an amino group, a sulfonamide group, an alkoxy group, Represents an aryloxy group, alkylthio group, arylthio group, acyl group, acyloxy group, sulfonyl group, carbamoyl group, alkoxycarbonyl group, or sulfamoyl group,
₁₁ and R ₁₂ or R ₁₄ and R ₁₅ may together form a carbocycle or a heterocycle, and R ₁₇ and R ₁₈ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. ,
The above R ₁₇ and R ₁₈ may together form a carbocycle or a heterocycle. ] 2. An image forming method, which comprises exposing the photographic light-sensitive material according to claim 1 twice or more to obtain an image.