JP2003043643A - Image forming method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method for a silver halide color photographic sensitive material excellent in dot reproducibility and white background variation even when continuous processing is carried out in the formation of a color image for proof reading (color proof). SOLUTION: In the image forming method for a silver halide color photographic sensitive material, in the silver halide color photographic sensitive material having at least one yellow image forming layer, at least one magenta image forming layer and at least one cyan image forming layer on a support, surface reflection density at 730 nm when up to the yellow image forming layer is formed on the support is >=1.1 and the surface reflection density after processing is <=0.1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for producing a proof color image (color proof) from a plurality of black and white halftone images obtained by color separation and conversion of halftone images in a color plate making / printing process. And a method for forming an image on a silver halide color photographic light-sensitive material for producing a color proof.
More specifically, the present invention relates to an image forming method for a silver halide color photographic light-sensitive material which is excellent in reproducibility of small dots and has little white background variation even when the exposure amount is changed.

[0002]

2. Description of the Related Art Conventionally, in color plate making / printing processes,
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 and a surprint method for forming a color image using a photopolymer or a diazo compound are known. There is.

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

On the other hand, the surprint method is a method of superimposing colored images on the same support. As this method, a colored image is obtained by toner development utilizing the adhesiveness of a photopolymerizable material. , For example, US Pat.
No. 582,327, No. 3,607,264 and No. 3,620,726.

Further, after transferring onto a support using a photosensitive coloring sheet and forming an image by exposure and development, another coloring sheet is laminated on this, and the same process is repeated to obtain a color proof. Examples of the method for forming the film are disclosed in JP-B-47-27441 and JP-A-56-501.
Known by No. 217.

Further, there is disclosed a method in which a photosensitive color sheet is used and each color image obtained by exposing and developing a corresponding color separation film is transferred and formed on one support.
No. 9-971140.

As the colorant of the toner and the coloring sheet for forming these images, a coloring material similar to the printing ink can be used, so that the color tone of the obtained color proof becomes close 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 time for the operation and a high production cost.

As a method for solving such drawbacks, a method of producing a color proof by using a silver salt color photographic light-sensitive material having a white support is disclosed in, for example, JP-A-56-56.
113139, 56-104335, 62-2
No. 80746, No. 62-280747, No. 62-28.
No. 0748, No. 62-280749, No. 62-280.
No. 750, No. 62-280849, and the like.

In these methods, a color-separated black-and-white image composed of a plurality of sheets converted from a color original into a color-separated halftone image is sequentially printed on one sheet of color paper by a method such as contact printing. A color image formed by a dye formed from a coupler by image development is used as a proof image.

In recent years, there has been a strong demand for the practical application of high-definition plate making and printing from the viewpoint of improving the image quality of printed matter. I haven't arrived. Further, in terms of obtaining a high-definition printing proof, as in the case of plate making / printing, there is a point to be improved. In particular, a color proof using a silver salt photographic system has a good small dot reproducibility, and further improvement in whiteness similar to that of a printed matter is desired.

On the other hand, Japanese Patent Application Laid-Open Nos. 1-260629, 61-233732 and 4-1632 disclose
A silver halide color photographic light-sensitive material having four emulsion layers of yellow, magenta, cyan and black, each having different spectral sensitivity, is described. However, the application to high-definition printing, which is a high-quality printing, and the printing by FM screening, is not mentioned at all, and there is no suggestion of the drawbacks due to the application, because it is only possible to obtain an image similar to a printed matter. Has not been done.

Further, in order to improve the image quality, it is necessary to improve the sharpness, and Japanese Patent Laid-Open No. 2000-26111 discloses a method of using various colloidal silver, but a sufficient effect can be obtained. Has not been done. Hardening the tone of a silver halide emulsion is also a necessary technique for achieving high image quality, and the effect is essential in a system using a direct positive emulsion. Japanese Unexamined Patent Publication No. 2000-214561 discloses metal ions having an electron trap depth of 0.2 eV or less.
The current situation is that direct positive emulsions have not achieved the effect of increasing the contrast.

[0014]

An object of the present invention is to produce a proof color image (color proof) from a plurality of black and white halftone images obtained by color separation and conversion of halftone images in a color plate making / printing process. Another object of the present invention is to provide an image forming method of a silver halide color photographic light-sensitive material suitable for producing a color proof. More specifically, it is an object of the present invention to provide an image forming method of a silver halide color photographic light-sensitive material which is excellent in reproducibility of small dots and has little white background variation even when the exposure amount is changed.

[0015]

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

1. In a silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer on a support, 730 nm when the yellow image forming layer is formed on the support. The surface reflection density at 1.1 or more,
An image forming method for a silver halide color photographic light-sensitive material, wherein the surface reflection density after development is 0.1 or less.

2. In a silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer on a support, the silver halide grains contained in the yellow image forming layer are The method for forming an image of a silver halide color photographic light-sensitive material, which further comprises a metal ion or a metal complex ion having an electron trap depth of 0.35 eV or more.

3. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer and an intermediate layer on a support, wherein the intermediate layer contains a hydroquinone derivative and the above-mentioned general formula (1). And a compound represented by the formula (4).

4. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer on a support, wherein the yellow image forming layer is an infrared light sensitive silver halide emulsion. And is located closer to the support than the blue-sensitive silver halide emulsion layer, and is located above the green-sensitive silver halide emulsion layer or the red-sensitive silver halide emulsion layer. An image forming method for a silver halide color photographic light-sensitive material.

The present invention will be described in more detail below. One of the preferred embodiments of the present invention is four kinds of photosensitive silver halide emulsions (hereinafter, also simply referred to as emulsions), which are an infrared photosensitive emulsion, a blue photosensitive emulsion, a green photosensitive emulsion and a red photosensitive emulsion.
A yellow image, a magenta image, a cyan image and a black image are formed. The combination of the four types of photosensitive emulsions and the image to be formed can be arbitrarily selected and configured as needed.

The emulsion for forming a black image is not particularly limited as long as it is an emulsion capable of forming a black image by a development process after image exposure. As a preferred example, a combination is formed as a black image forming layer containing an emulsion and a black coupler.
Also, a plurality of couplers having different maximum wavelengths can be used instead of the black coupler. It is also one of the preferable examples in which the emulsion contributes to the image formation of a plurality of layers and a black image is formed by a combination of a plurality of images resulting from the development of the emulsion. Examples of forming a black image by combining a plurality of images include, for example, a blue image (for example, a magenta image and a cyan image) that contains the emulsion in a yellow image layer for forming a yellow image and is a complementary color of the yellow image. Is formed at the same time to form a blue image). The forming layer also contains the emulsion, and the emulsion is developed to form a black image. Further, a black image is similarly formed when the emulsion is contained in the magenta image forming layer and its complementary color image forming layer, or when the emulsion is contained in the cyan image forming layer and its complementary color image forming layer. be able to.

In another preferred example, the emulsion is contained in any of a yellow image forming layer, a magenta image forming layer and a cyan image forming layer, and a black image is formed by developing the emulsion. Is. In that case, the yellow image forming layer, the magenta image forming layer and the cyan image forming layer may or may not contain any other emulsion.

Each of the yellow image-forming, magenta image-forming, and cyan image-forming silver halide emulsion layers according to the present invention may be a single layer or a plurality of layers. Also, the order of coating from the support can be arbitrarily selected.

Blue-sensitive, green-sensitive, red-sensitive and infrared-sensitive emulsions have a sensitivity in the spectral sensitivity region of any emulsion that is at least 6 times higher than the sensitivity at wavelengths of other emulsions. High is desirable. Where sensitivity is
It is the reciprocal of the exposure amount required to bring the density of the image forming layer to the maximum density of -0.3. More preferably, the sensitivity is 8 times or more higher.

The photosensitive emulsions having different spectral sensitivities in the present invention can be realized by selecting from conventionally known spectral sensitizing dyes and optically sensitizing them.

Another embodiment of the present invention is a method of forming yellow, magenta and cyan images by using three types of photosensitive emulsions of infrared light-sensitive, green light-sensitive and red light-sensitive emulsions. is there. The combination of the three types of photosensitive emulsions and the image to be formed can be arbitrarily selected. This form is particularly effective in that it can be combined with an inexpensive semiconductor laser light source.

The silver halide color photographic light-sensitive material according to the present invention is preferably a positive type silver halide color photographic light-sensitive material (hereinafter also referred to as a positive-type light-sensitive material).
This positive type photosensitive material includes a direct positive type and a color reversal type photosensitive material. Further, a photosensitive material using a so-called silver dye bleaching method, a photosensitive material using a color diffusion transfer method, and the like, which simultaneously bleach a dye to form a positive image when bleaching silver produced imagewise, are also included in the present invention. It is included in the light-sensitive material.

The grain size of each emulsion of the light-sensitive material according to the present invention is
It can be selected from a wide range in consideration of the required performance characteristics such as sensitivity, sensitivity balance, color separability, sharpness, and graininess.

In the present invention, a silver halide emulsion layer, an intermediate layer, a protective layer and the like are laminated and coated sequentially from a support. As a coating method, there are known methods such as curtain coating method and slide hopper method. preferable.

In the present invention, when the yellow image forming layer is formed on the support, the surface reflection density at 730 nm is 1.1 or more, and when the yellow image forming layer is formed on the support after the development treatment. The surface reflection density at 730 nm is 0.1 or less.

The surface reflection density as used in the present invention means that the surface at the stage of coating from the support to the yellow image-containing layer has a wavelength of 7 with a color analyzer 607 (manufactured by Hitachi).
The reflection density at 30 nm is measured. The surface reflection density at 730 nm when the yellow image forming layer is formed on the support after the development treatment is obtained by performing the following development treatment and then measuring by the same method.

(Development processing) Treatment process temperature time Development 37 ℃ 120 seconds Bleach-fixing 35 ℃ 45 seconds Stabilization treatment 25-35 ° C 45 seconds Drying 50-85 ° C 40 seconds The stabilization treatment was a countercurrent system with a three-tank configuration.

(Development Processing Solution) As the color developing solution, bleach-fixing solution and stabilizing solution used in the above-mentioned development processing, JP-A-7-8 is used.
Each processing solution described in paragraph numbers [0166] to [0168] of No. 8359 can be used.

One feature of the present invention is that the surface reflection density at 730 nm when the yellow image forming layer is formed on the support before development is 1.1 or more, but preferably 1.3. ~ 1.6. Further, the surface reflection density at 730 nm when the yellow image forming layer is formed on the support after the development treatment is 0.1 or less, but preferably 0.05 to 0.1.

As a means for achieving the above-mentioned surface reflection density, it is achieved by appropriately selecting and containing a coloring substance such as a dye having absorption at 600 to 800 nm or black colloidal silver.

The light-sensitive material according to the present invention may contain a water-soluble dye in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers. Further, in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers, a carboxyl group,
A dye having at least one of a sulfonamide group and a sulfamoyl group can be contained in a solid dispersion.

Examples of the dye having at least one of the carboxyl group, the sulfamoyl group and the sulfonamide group are represented by formulas [I] to [IX] described on pages 14 to 16 of JP-A-6-95283. The compounds mentioned can be mentioned.

Among the compounds represented by the above general formulas [I] to [IX], specific examples of the dyes represented by the general formulas [I] to [VIII] are described, for example, in JP-A-4-18545. Thirteen
To Exemplified Compounds I-1 to VIII-7 described on page 35 can be mentioned, but the invention is not limited thereto.

The layer containing the dye or colloidal silver is not particularly limited, but it is preferably contained in the non-photosensitive layer disposed between the support and the image forming layer closest to the support. The content of the above dye is 1 to 300 mg / m ²
Is preferred. Also, colloidal silver is 20 to 100 mg / m
² is preferably contained.

In the light-sensitive material according to the present invention, the thickness on the side having the silver halide emulsion is preferably 10 to 20 μm, more preferably 10 to 15 μm. The film thickness between the layer containing the infrared-sensitive emulsion and the support is 3 to 1
It is preferably 5 μm. That is, if it is thinner than 3 μm, the whiteness is deteriorated, and if it is thicker than 15 μm, the dot reproducibility is deteriorated, which is not preferable.

As the silver halide emulsion used in the light-sensitive material of the present invention, a surface latent image type silver halide emulsion which forms a latent image on the surface by imagewise exposure is used to develop a negative image. You may use the silver halide emulsion. Further, using an internal latent image type silver halide emulsion in which the grain surface is not previously fogged, after image exposure, a fog treatment (nucleation treatment) is performed, and then surface development is performed, or after the image exposure, a fog treatment is performed. Those which can directly obtain a positive image by carrying out surface development while applying are also preferably used. The internal latent image type silver halide emulsion referred to in the present invention includes silver halide grains containing silver halide crystal grains mainly having a photosensitive nucleus inside and a latent image being formed inside the grain by exposure. Of emulsion.

The above-mentioned fog treatment may be carried out by exposing the entire surface, or by chemically using a fog agent, or by using a developing solution having a strong reducing power, and further heat treatment or the like. May be

The above-mentioned whole surface exposure is carried out by immersing or moistening the imagewise exposed light-sensitive material in a developing solution or other aqueous solution, 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 photosensitive 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 depends on the photosensitive material used,
Depending on the development processing conditions, the type of light source used, etc., it can be varied over a wide range so as to finally obtain the best positive image.

Further, it is most preferable that the exposure amount of the whole surface exposure gives a predetermined range of exposure amount in combination with the photosensitive material. Usually, if the exposure amount is excessively increased, the minimum density is increased or desensitized, and the image quality tends to be deteriorated.

The fog agent which can be used in the light-sensitive material of the present invention is, for example, JP-A-6-95283, 18.
It is preferable to use the technique described in page 39, right column, line 39 to page 19, left column, line 41.

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

Particularly preferably, the coated silver amount is about 1 to 3.5.
exposing a portion of the sample coated on the transparent support in the range of g / m ² to a light intensity scale for a defined period of time from about 0.1 second to about 1 second; When the surface developing solution A described in paragraph No. [0134] of JP-A-2000-89418 for developing only the surface image of a grain containing substantially no silver halide solvent is developed at 20 ° C. for 4 minutes, Another part of the same emulsion sample was similarly exposed and developed at 20 ° C. for 4 minutes using an internal developer B described in paragraph No. [0134] of JP-A-2000-89418 for developing an image inside the grain. It is an emulsion showing a maximum density that is not more than 1/5 of the maximum density obtained in some cases. More preferably,
The maximum density obtained using the surface developer A is not larger than 1/10 of the maximum density obtained with the internal developer B.

The internal latent image type silver halide emulsions preferably used in the light-sensitive material of the present invention include those prepared by various methods. For example, US Pat. No. 2,59
Conversion-type silver halide emulsions described in US Pat. No. 2,250; Internal chemistry described in US Pat. Nos. 3,206,316, 3,317,322 and 3,367,778. Silver halide emulsions with sensitized silver halide grains; US Pat. No. 3,271,15
No. 7 and No. 3,447,927, emulsions containing silver halide grains containing polyvalent metal ions; the dopants described in US Pat. No. 3,761,276. A silver halide emulsion in which the surface of the contained silver halide grains is weakly chemically sensitized; JP-A-50-852.
No. 4, No. 50-38525 and No. 53-2408, and silver halide emulsions composed of grains having a laminated structure; Others are described in JP-A Nos. 52-156614 and 55-127549. Examples thereof include silver halide emulsions.

The shape of the silver halide grains used in the present invention is a cube, an octahedron, a tetrahedron composed of a mixture of (100) plane and (111) plane, a shape having a (110) plane, a spherical shape, a tabular shape and the like. It may be any of Average particle size is 0.0
Those having a thickness of 5 to 3 μm are preferably used. The particle size distribution is
A monodisperse emulsion having uniform grain size and crystal habit may be used, or an emulsion having no uniform grain size or crystal habit may be used, but a monodisperse silver halide emulsion having uniform grain size and crystal habit is preferable.

In the present invention, the monodisperse silver halide emulsion means that the mass of silver halide contained in the grain size range of ± 20% around the average grain size r _m is 60 of the total mass of silver halide grains. % Or more, preferably 70% or more, more preferably 80% or more. Here, the average particle size r _m 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 (significand 3 digits, the lowest digit is rounded to 4). The grain size r _i here is the diameter of a spherical silver halide grain, or the diameter of the projected image converted to a circle of the same area in the case of a grain having a shape other than spherical. is there. The grain size can be obtained by, for example, enlarging a silver halide grain by an electron microscope at a magnification of 10,000 to 50,000 and photographing the grain diameter of the grain or the area at the time of projection. In addition,
It is assumed that the number of measured particles is 1000 or more indiscriminately.

In the present invention, a particularly preferred highly monodisperse emulsion is one having a distribution width of 20% or less defined by (particle size standard deviation / average particle diameter) × 100 = distribution width (%). Is.
Here, the average particle size and the particle size standard deviation are the particle size r defined above.
_It shall be obtained from _i .

In the present invention, the monodisperse emulsion is 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. You can In determining the addition rate, JP-A-54-48521,
Reference can be made to No. 58-49938. As a method for obtaining a more advanced monodisperse emulsion, JP-A-60-12293 is used.
The growth method in the presence of the tetrazaindene compound disclosed in No. 5 can be applied. It is also preferable to add two or more of the monodisperse emulsions to the same color-sensitive layer.

In the present invention, the grain size of the silver halide emulsion used in the image forming layer is determined in consideration of the required performance, particularly various characteristics such as sensitivity, sensitivity balance, color separation, sharpness and graininess. , Can be determined from a wide range.

In one of the preferred embodiments of the present invention, the grain size of the silver halide emulsion is 0.
1-0.6 μm, 0.15-0.8 μm for green photosensitive emulsion
m, and a blue-sensitive emulsion, a range of 0.3 to 1.2 μm can be preferably used.

In the silver halide color photographic light-sensitive material according to the present invention, the silver halide emulsion used contains a compound selected from metal ions having a depth of electron trap of 0.35 eV or more and metal complex ions. The feature is to do. The value of the depth of the electron trap is, for example,
R. S. Eachus, R.A. E. Grave and M.D. T.
Ols Phys. Stat. Eighth of Sol (b)
Volume 8, page 705 (1978), can be determined by a kinetic method by ESR.
The depth of the electron trap depends on the type of central metal ion, the type of ligand, the symmetry of the point group of the complex (0h, D4h, C4v
Etc.) and the halogen composition of the silver halide host grains. The depth of the electron trap is determined by whether the lowest unoccupied orbital energy level of an electron of a metal ion or a metal complex ion is lower or higher than the bottom of the conduction band of silver halide.
When the energy level is higher than the bottom of the conduction band of silver halide, the electron is loosely bound by the Coulomb force of the central metal ion, resulting in a shallow electron trap. Conversely, when the energy level is low, the energy from the conduction band is reduced. The difference corresponds to the depth of the electron trap, resulting in a relatively deep electron trap.

The present invention is characterized in that the depth of the relatively deep electron trap is 0.35 eV or more.
It is preferably 0.5 to 0.8 eV.

In the present invention, preferred examples of metal ions or metal complex ions are halide ion ligands or thiocyanate ion ligands, and Ir, Rh, R.
An ion containing u or Pb; an ion containing at least one kind of nitrosyl ligand and Ru; an ion containing a cyan ligand and Cr; Among these, [IrCl ₆ ] ³⁻ , [IrBr ₆ ] ³⁻ , [Ir (SCN) ³
₆ ] ³⁻ , [IrI ₆ ] ³⁻ , [RhCl ₅ (H ₂ O)] ²⁻ ,
[RhCl ₄ (H ₂ O) ₂ ] ^- , [RuCl ₅ (N
O)] ^2- , [Cr (CN) ₆ ] ^3- , [RhCl ₆ ] ^3- ,
[RhBr ₆ ] ³⁻ , [PbCl ₆ ] ^{5− and the} like are used.

In the light-sensitive material according to the present invention, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or a silver halide emulsion layer is added. It is preferable to add them to improve fog and the like. As a compound for this, a hydroquinone derivative is preferable,
More preferably, it is a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. A particularly preferable compound is the compound represented by the general formula II described in JP-A-4-133056, and the specification of JP-A-4-133056
Compounds II-1 to II-14 and 17 described on pages 14 to 17
The compound 1 described in the page is mentioned.

The invention according to claim 3 is characterized in that the silver halide color photographic light-sensitive material contains the hydroquinone derivative and the compound represented by the general formula (1).

The compound represented by the general formula (1) will be described below. In the general formula (1), the substituent represented by R ₁ , R ₂ and R ₃ is a linear or branched alkyl group (eg, methyl group, ethyl group, i-propyl group, t-butyl group). , Dodecyl group and i-hexylnonyl group), cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, bicyclo [2,2,1] heptyl group and adamantyl group), aryl group (for example, phenyl group, 1 -Naphthyl group, 9-anthranyl group, etc.) and the like, and these substituents represented by R ₁ , R ₂ and R ₃ may further have a substituent, and R ₁ , R ₂ and R ₃
And a alkenyl group having the same meaning as the substituent, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a sulfonylamino group, a sulfamoylamino group, an acylamino group, a heterocyclic oxy group, a urethane group, and a ureido group. 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. p, q and r represent 0 or 1.

In the general formula (1), the substituent represented by R ₁ , R ₂ and R ₃ preferably has 6 to 1 carbon atoms.
It is an alkyl group of 2 and 0 is preferable as an integer represented by p, q and r.

The substituents represented by R ₁ , R ₂ and R ₃ in the general formula (1) are particularly preferably R ₁ , R ₂ and R 3.
₃ is an octyl group at the same time.

Specific examples of the high boiling point organic solvent represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited thereto.

[0065]

[Chemical 2]

[0066]

[Chemical 3]

[0067]

[Chemical 4]

The compound represented by the general formula (1) is preferably added to the silver halide color photographic light-sensitive material in an amount of 0.2 to 10 g / m ² , more preferably 0.4 to 8 g. / M ² content.

Among the compounds represented by the general formula (1), preferred compounds are compounds having a molecular weight of 400 or more, more preferably compounds having a molecular weight of 450 or more, particularly preferably compounds having a molecular weight of 500 or more.

The yellow image forming layer, the magenta image forming layer and the cyan image forming layer in the light-sensitive material according to the present invention contain silver halide emulsions having different spectral sensitivity wavelength regions from each other, and the above yellow, magenta, and A silver halide having a spectral sensitivity having a common portion with at least one of the cyan image forming layers and emulsions having different spectral sensitivity wavelength regions contained in the yellow, magenta and cyan image forming layers, respectively. It is preferable that an emulsion is contained. Further, a black image forming layer containing a silver halide emulsion having a spectral sensitivity distribution different from that of the silver halide emulsions of the yellow, magenta and cyan image forming layers is provided, and the silver halide emulsion having a different spectral sensitivity distribution is yellow. It is particularly preferable to provide a layer containing a silver halide emulsion which is contained in any of the magenta and cyan image forming layers to form a color image of the containing layer and a complementary color image.

The silver halide color photographic light-sensitive material according to the present invention has a yellow image forming layer, a magenta image forming layer and a cyan image forming layer, and the yellow image forming layer contains an infrared sensitive silver halide emulsion. Preferably. The infrared-sensitive silver halide emulsion layer is closer to the support than the blue-sensitive silver halide emulsion layer, and is higher than the green-sensitive silver halide emulsion layer or the red-sensitive silver halide emulsion layer. Preferably there is. Considering the effects of both irradiation and halation, the above-mentioned arrangement is preferable as the infrared-sensitive silver halide emulsion layer. The order of preferred layers is from the side closer to the support to a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer, an infrared light-sensitive silver halide emulsion layer, and a blue light-sensitive silver halide emulsion layer. In addition to these, an intermediate layer, a filter layer, a protective layer, and the like can be arranged if necessary.

The light-sensitive material according to the present invention preferably contains a nitrogen-containing heterocyclic compound having a mercapto group.
As a preferable compound, JP-A-6-95283 19
General formula [XI] described in page 20, right column, lines 20 to 49, particularly preferably, general formula [XII], general formula [XIII] or general formula [XII], page 20, left column, line 5 to page 20, right column, line 2 XIV]. Specific examples of the compound include, for example, JP-A-64-7333.
Exemplified compounds (1) to (39) described in No. 8, pages 11 to 15
Can be mentioned.

The addition amount of the above-mentioned mercapto compound may be appropriately changed depending on the kind of the compound used and the layer to be added, and when it is added to the silver halide emulsion layer, it is generally 10 ⁻ per mol of silver halide. ^{The amount is in} the range of ⁸ to 10 ^-2 mol, more preferably 10 ^-6 to 10 ^-3 mol.

Gelatin is preferably used as a binder in the light-sensitive material of the present invention. In particular, in order to remove the coloring component of gelatin, the gelatin extract was subjected to hydrogen peroxide treatment, or the raw material ossein was extracted with hydrogen peroxide treatment, or was produced from uncolored raw bone. Gelatin whose transmittance is improved by using ossein is preferable. The gelatin may be any of alkali-treated ossein gelatin, acid-treated gelatin, gelatin derivative and modified gelatin, and alkali-treated ossein gelatin is particularly preferable. The gelatin transmittance is preferably 70% or more when a 10% solution is prepared and the transmittance is measured at 420 nm with a spectrophotometer.

Jelly strength of gelatin (by the Paggy method)
Is preferably 250 g or more, particularly preferably 2
It is 70 g or more.

The ratio of the alkali-treated ossein gelatin to the total coated gelatin is not particularly limited, but it is preferable to use a large ratio, and specifically, at least 20-.
A preferable effect can be obtained by using it in a ratio of up to 100%.

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

As a hardener for these binders, a vinyl sulfone type hardener or a chlorotriazine type hardener is preferably used alone or in combination.
It is also preferable to use the compounds described in Nos. 1-249054 and 61-245153. Further, in order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer. .

As the magenta coupler used in the light-sensitive material according to the present invention, the compound represented by the general formula [M-1] described in JP-A-6-95283, page 7, right column has a spectral absorption characteristic of a coloring dye. Well preferred. Specific examples of preferable compounds include Exemplified Compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Further, as other specific examples, compounds M-1 to M-61 described on pages 6 to 21 of EP-A-273,712 and exemplary compounds described on pages 36 to 92 of 235913. 1 to 223 other than the above representative examples.

In the present invention, as the magenta coupler, a plurality of types of magenta couplers can be used in combination, and usually 1 × 10 ^-2 to 1 mol per mol of silver halide,
Preferably, it can be used in the range of 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol.

In the light-sensitive material according to the present invention, the maximum absorption wavelength (λ _max ) of the spectral absorption of the magenta image formed.
Is preferably 530 to 560 nm, and λ
_L0.2 is preferably ₅₈₀ to 635 nm.

Here, the photosensitive material according to the present invention is used.
Λ of spectral absorption of magenta image _L0.2In the following way
It is the quantity to be measured.

That is, the density of the ND filter is adjusted so that the maximum value of the absorbance of the magenta image at the time of measuring the spectral absorption is 1.0 by applying green light through the ND filter. λ _L0.2 means a wavelength longer than the wavelength at which the maximum absorbance is 1.0 on the spectral absorbance curve of this magenta image and at which the absorbance is 0.2.

The magenta image forming layer of the light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. PKa of these couplers
The difference is preferably within 2 and more preferably within 1.5. Preferred yellow couplers contained in the magenta image-forming layer according to the present invention are disclosed in JP-A-6-
No. 95283, the general formula [Y-I
a] is a coupler. The general formula [Y
Among the couplers represented by [-1], particularly preferable ones are those of the coupler represented by [M-1] when combined with the magenta coupler represented by the general formula [M-1] described in the same publication. A coupler having a pKa value not lower than 3 by less than pKa.

Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283, and pages 13 to 17 of JP-A-2-139542. Compounds (Y-1) to (Y-
58) can be preferably used, but is not limited to these.

In the light-sensitive material according to the present invention, as the cyan coupler contained in the cyan image forming layer, known phenol type, naphthol type or imidazole type couplers can be used. For example, a phenol-based coupler substituted with an alkyl group, an acylamino group, a ureido group, or the like, 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 are typical. To be done.
Of these, preferred compounds include JP-A-6-9528.
The general formulas [C-I] and [C-II] described in No. 3, page 13 are mentioned.

The cyan coupler is usually used in a silver halide emulsion layer in an amount of 1 × 10 ^-3 to 1 per mol of silver halide.
It can be used in an amount of 1 mole, preferably 1 × 10 ^-2 to 8 × 10 ^-1 mole.

In the light-sensitive material according to the present invention, the yellow coupler contained in the yellow image forming layer is
Known acylacetanilide type couplers and the like can be preferably used.

Specific examples of the yellow coupler include, for example, Y described in JP-A-3-241345, pages 5 to 9.
-I-1 to Y-I-55, or
Y-described on pages 11 to 14 of JP-A-3-209466
The compounds represented by 1 to Y-30 can also be preferably used. Further, couplers represented by the general formula [Y-I] described on page 21 of JP-A-6-95283 can also be mentioned.

In the light-sensitive material according to the present invention, the formed yellow image preferably has a spectral absorption λ _max of 425 nm or more and a λ _L0.2 of 515 nm or less. Here, λ _L0.2 is defined as in the case of a magenta image.

The yellow coupler can be used usually in the image forming layer in the range of 1 × 10 ^-2 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 ^-1 mol, per mol of silver halide. .

In order to adjust the spectral absorption characteristics of the formed magenta image, cyan image and yellow image, it is preferable to add a compound having a color tone adjusting action. As the compound for this, a compound represented by the general formula [HBS-I] or [HBS-II] described on page 22 of JP-A-6-95283 is preferable, and more preferably the general formula [HBS
-II].

An anti-fading agent can be used in combination with each of the magenta, cyan and yellow couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like.
Preferred compounds include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, and the general formula described in JP-A-3-174150.
Phenolic compounds represented by IIIB, JP-A-64-9
Amine compounds represented by the general formula A described in JP-A-0445, and general formula XI described in JP-A-62-182741.
The metal complex represented by I, XIII, XIV or XV is particularly preferable for the magenta dye. Also, Japanese Patent Laid-Open No. 1-196049
Compounds represented by the general formula I ′ described in JP-A No.
The compound represented by the general formula II described in JP-A-11417 is particularly preferable for yellow and cyan dyes.

In the light-sensitive material according to the present invention, the oil-in-water type emulsion dispersion method used for adding a coupler and other oil-soluble organic compounds is usually carried out by adding the above compound to a boiling point of 1: 1.
A water-insoluble high-boiling point organic solvent having a temperature of 50 ° C. or higher and, if necessary, a low-boiling point and / or water-soluble organic solvent are dissolved together and dissolved, and emulsified and dispersed in a hydrophilic binder such as gelatin aqueous solution using a surfactant. . As the dispersing means, for example, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. A step of removing the low boiling point organic solvent may be added after or at the same time as the dispersion. Examples of the high-boiling-point organic solvent that can be used to dissolve and disperse the coupler and the like include, for example, dioctyl phthalate, diisodecyl phthalate, dibutyl phthalate and other phthalates, tricresyl phosphate, trioctyl phosphate and the like phosphoric acid. High boiling organic solvents such as esters and phosphine oxides such as trioctylphosphine oxide can also be preferably used. Also, as the dielectric constant of the high boiling point organic solvent,
It is preferably from 3.5 to 7.0. It is also possible to use two or more high boiling point organic solvents in combination.

In the light-sensitive material according to the present invention, a compound preferable as a surfactant used for dispersing the photographic additives and adjusting the surface tension at the time of coating is a hydrophobic group having 8 to 30 carbon atoms in one molecule. And those containing a sulfonic acid group or a salt thereof. Specifically, Japanese Patent Laid-Open No. 64-2
Exemplary compounds A-1 to A-11 described in No. 6854 are listed. Further, a surfactant having a fluorine atom substituted in the alkyl group is also preferably used.

The dispersion prepared by the above method is usually added to a coating solution containing a silver halide emulsion. The shorter the time, the better, 10 each
The time is preferably within 3 hours, more preferably within 3 hours, and further 2
It is more preferably within 0 minutes.

In the light-sensitive material according to the present invention, a compound that reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or is added to the image-forming layer. It is preferable to reduce fog and the like. The compound for this purpose is preferably a hydroquinone derivative, and more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. A particularly preferable compound is the compound represented by the general formula II described in JP-A-4-133056, and the compound II-1 described on pages 13 to 14 of the same.
To II-14 and Compound 1 described on page 17.

In the light-sensitive material of the present invention, it is preferable to add an ultraviolet absorber to prevent static fog and improve the light resistance of dye images. Examples of preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are compounds represented by the general formula III-3 described in JP-A-1-250944, and JP-A-64-666.
A compound represented by formula III described in JP-A-46-46, JP-A-63
-187240 Exemplified Compounds UV-1L to UV-
27L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

The silver halide in the light-sensitive material of the present invention can usually be optically spectrally sensitized with a sensitizing dye. The combined use of sensitizing dyes used for supersensitization such as internal latent image type silver halide emulsions and negative type silver halide emulsions is also useful for the silver halide emulsion according to the present invention. Regarding sensitizing dyes, Research Disclosure (Research Disclo)
(hereinafter, abbreviated as RD) 15162 and 176
No. 43 can be referred to.

To the light-sensitive material according to the present invention, it is preferable to add a compound for adjusting the gradation of the feet. As a preferable compound, the compound represented by the general formula [AO-II] described on page 17 of JP-A-6-95283 is preferable. Examples of preferable compounds include Exemplified Compounds II-1 to II-8 described on page 18 of the same publication.

The addition amount of the compound represented by the general formula [AO-II] is preferably 0.001 to 0.50 g / m ² , and more preferably 0.005 to 0.20 g / m ² . The compound may be used alone or in combination of two or more kinds. Furthermore, a quinone derivative having 5 or more carbon atoms is [AO-II]
It can also be used by adding it to the compound. However, in all of these cases, the amount used is 0.0
It is preferably in the range of 01 to 0.50 g / m ² .

In order to improve the whiteness, it is preferable to add a fluorescent whitening agent to the light-sensitive material or the developing solution according to the present invention.

When developing the light-sensitive material of the present invention,
Color developing solution, bleach-fixing solution, and stabilizing solution are continuously developed while replenishing replenishing color developing solution, replenishing bleaching solution, replenishing fixing solution, replenishing bleach-fixing solution, replenishing stabilizing solution, etc. can do.

In the development processing of the light-sensitive material according to the present invention, examples of the color developing agent that can be used in the color developing solution include aminophenols and phenylenediamines, and p-phenylenediamines are preferable and Include 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, 4-amino-3-methyl-N-ethyl-N-
Color developing agents such as (γ-hydroxypropyl) aniline can be mentioned.

In addition, as an auxiliary developing agent, a conventional silver halide developing agent, for example, polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, or the like, or It may contain a mixture, specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
It is also possible to include all or part of these developing agents such as pyrazolidone and ascorbic acid in the light-sensitive material in advance so that they act on the silver halide during immersion in a high pH aqueous solution.

In the light-sensitive material according to the present invention, the color developer used may further contain a specific antifoggant and development inhibitor, or those developer additives may be added to the constituent layers of the light-sensitive material. It may be optionally incorporated therein.

In the present invention, the color developing solution is adjusted to an arbitrary pH.
Although it can be used in a range, the pH thereof is preferably 9.5 to 13.0, and more preferably pH 9.8 to 12.0, from the viewpoint of rapid processing.

The processing temperature for color development is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature is, the shorter the treatment time is, which is preferable. However, it is preferable that the treatment liquid is not so high in view of the stability of the treatment liquid.

In the color developing solution, in addition to the color developing agent,
Known developer component compounds may be added, for example, an alkaline agent having a pH buffering action, chloride ion,
Development inhibitors such as benzotriazoles, preservatives and chelating agents are used.

The silver halide color photographic light-sensitive material according to the present invention may be subjected to bleaching treatment and fixing treatment after color development, and the bleaching treatment may be conducted simultaneously with the fixing treatment. After the fixing process, the stabilization process is usually performed and the pH is adjusted with various alkaline agents.
It is preferable that the pH of the film surface of the silver halide color photographic light-sensitive material after the preparation is dried to be 7 or less.

As an example of the method for measuring the film surface pH, the photosensitive material is allowed to stand in an atmosphere of 23 ° C. and 55% RH for 24 hours, and then two drops of 0.3 M potassium nitrate aqueous solution are dropped on the surface with a pipette. , Toa Denpa Co., Ltd. membrane surface pH electrode (GST-5213F) are brought into contact, equilibrated for 3 minutes, and the pH value can be determined.

Further, known photographic additives can be used in the light-sensitive material according to the present invention. Examples thereof include compounds described in RD17643 and RD18716 shown in Table 1.

[0113]

[Table 1]

The reflective support used in the light-sensitive material according to the present invention is preferably a base paper, which is laminated on both sides with a polyolefin resin.

The base paper used as the support is generally
It can be selected from the raw materials used for photographic printing paper, and examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for paper making. Generally, a natural pulp mainly composed of a softwood pulp, a hardwood pulp, a mixed pulp of a softwood pulp and a hardwood pulp, etc. can be widely used.

The support may further contain additives such as a sizing agent, a fixing agent, a toughening agent, a filler, an antistatic agent and a dye, which are generally used in papermaking. An agent, a surface-strengthening agent, an antistatic agent, etc. may be appropriately applied to the surface.

The reflective support is usually 50 to 300 g / m ^2.
Of which the surface is smooth and whose both surfaces are laminated is a resin such as ethylene, polyethylene terephthalate, α-olefins, for example, a homopolymer such as polypropylene, or at least 2 of the above olefins.
It is possible to select from a copolymer of one kind or a mixture of at least two kinds of these various kinds of polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin to be laminated on the reflective support is not particularly limited, but normally one in the range of 20,000 to 200,000 is used.

In the light-sensitive material according to the present invention, the polyolefin resin coating layer on the side of the reflective support on which the silver halide emulsion is coated is preferably 25 to 50 μm, more preferably 25 to 35 μm.

The polyolefin layer used for laminating the back surface side (the reflection side of the surface on which the image forming layer is provided) of the reflective support is usually a melt-laminated mixture of a low density polyethylene and a high density polyethylene. .
This layer is often matted.

In forming the laminate on the front and back of the support in the light-sensitive material of the present invention, generally, the density of the resin layer on the front side is set to be slightly higher than that on the back side in order to increase the flatness of the developed light-sensitive material in a normal environment. Alternatively, a means such as increasing the amount of laminating on the back side than on the front side is used.

In general, the front and back surfaces of the reflective support can be laminated by forming the polyolefin resin composition on the support by melt extrusion coating. In addition, it is preferable to perform corona discharge treatment, flame treatment, or the like on the surface of the support, or on both the front and back surfaces, if necessary. Further, a sub-coat layer for improving the adhesiveness to the image forming layer or the auxiliary layer is formed on the surface of the surface laminate layer, or a back coat layer for improving the printability and antistatic property on the laminate layer on the back surface. It is preferable to provide.

The polyolefin resin used for laminating the support surface (the surface on which the emulsion layer is provided) of the light-sensitive material of the present invention is preferably 13 to 20% by mass, more preferably 15 to 20% by mass of a white pigment dispersed therein. Mixed. As the white pigment, an inorganic and / or organic white pigment can be used, preferably an inorganic white pigment. Examples of such a white pigment include alkaline earth metal sulfates such as barium sulfate and calcium carbonate. Alkaline earth metal carbonates,
Examples thereof include finely divided silicic acid, synthetic silicate silicas, calcium silicate, alumina, hydrated alumina, titanium oxide, zinc oxide, talc, clay and the like. Of these, barium sulfate, calcium carbonate and titanium oxide are preferable, and barium sulfate and titanium oxide are more preferable.
Titanium oxide may be rutile type or anatase type,
Further, those whose surface is coated with metal oxide such as hydrous alumina and hydrous ferrite are also used.

In addition, it is preferable to add an antioxidant, a colored pigment for improving whiteness, and a fluorescent whitening agent.

Further, it is preferable to coat a hydrophilic colloid layer containing a white pigment on the reflective support because the sharpness is improved. As the white pigment, the same white pigment as described above can be used, but titanium oxide is preferable. It is more preferable to add a hollow fine particle polymer or a high-boiling point organic solvent to the hydrophilic colloid layer containing a white pigment because the sharpness and curl resistance can be improved.

As the reflective support used in the light-sensitive material according to the present invention, a synthetic resin film support such as polypropylene whose surface is further coated with polyolefin can be used.

The thickness of the reflective support is not particularly limited,
Those having a thickness of 80 to 160 μm are preferably used, and 90 to
The thickness of 130 μm is more preferable.

The surface shape of the reflective support may be smooth or may have an appropriate surface roughness, but it is preferable to select a reflective support having a gloss close to that of a printed matter. For example, the average surface roughness SRa specified in JIS-B0601-1976 is 0.30 to 3.0 μm.
It is preferred to use a white support which is

In the light-sensitive material of the present invention, it is preferable that the image forming surface has a surface roughness of 0.30 to 3.0 μm. Therefore, in the constituent layer on the image forming surface side of the light-sensitive material. Can contain a matting agent. The layer to which the matting agent is added includes an image forming layer, a protective film, an intermediate layer and an undercoat layer, which may be added to a plurality of layers, and is preferably the uppermost layer of the light-sensitive material.

The surface gloss of the light-sensitive material of the present invention on the image forming layer side preferably has a gloss close to that of a printed matter,
For example, JIS-Z874 on the surface after the processing of the image forming layer is performed.
Gloss G _S (60 °) measured by the method specified in 1.
Is preferably 5 to 60.

[0131]

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

Example 1 << Preparation of Silver Halide Emulsion >> (Preparation of Emulsion EM-P1) While controlling an aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride were prepared. An aqueous solution containing (KBr: NaCl = 95: 5 in a molar ratio) was simultaneously added by a 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 appropriately 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 a control double jet method. Then, a shell was formed until the average particle size became 0.42 μm. At that time, p so that a cubic shape is obtained as the particle shape.
H and pAg were controlled appropriately.

Then, after washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P1. Emulsion E
The distribution of M-P1 was 8%.

(Preparation of Emulsion EM-P2) 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). ) And an aqueous solution containing) were simultaneously added by a control double jet method to obtain a cubic silver chlorobromide core emulsion having a grain size of 0.18 μm. At that time, p so that a cubic shape is obtained as the particle shape.
H and pAg were controlled appropriately.

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 a control double jet method. Then, a shell was formed until the average particle size became 0.25 μm.
At that time, pH and pAg were appropriately controlled so that a cube was obtained as a particle shape.

Next, after washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P2. Emulsion EM
The breadth of distribution of P2 was 8%.

(Preparation of Blue-Sensitive Silver Halide Emulsion) The emulsion EM-P1 prepared above was sensitized optimally by adding the sensitizing dye BS-1 and then the stabilizer ST-1 was added per mol of silver. 100 mg was added to prepare a blue-sensitive emulsion EM-B1.

(Preparation of Green-Sensitive Silver Halide Emulsion) Same as blue-sensitive emulsion EM-B1 except that sensitizing dye GS-1 was added to emulsion EM-P1 prepared above for optimum color sensitization. To produce a green photosensitive emulsion EM-G1.

(Preparation of Red-Sensitive Silver Halide Emulsion) Emulsion EM-P2 prepared above was mixed with sensitizing dyes RS-1 and RS.
-2 was added for optimum color sensitization, but blue sensitive emulsion EM
A red photosensitive emulsion EM-R1 was prepared in the same manner as in -B1.

(Preparation of infrared-sensitive silver halide emulsion) To the emulsion EM-P2 prepared above, sensitizing dyes IRS-1 and IRS-2 were added for optimum color sensitization, and the inhibitor AF-1 was added.
Infrared photosensitive emulsion E was prepared in the same manner as blue photosensitive emulsion EM-B1 except that (sodium ascorbate monohydrate) was added.
M-IR1 was produced.

The structures of the additives used for the preparation of each emulsion are shown below. ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene

[0143]

[Chemical 5]

[0144]

[Chemical 6]

<< Production of silver halide color photographic light-sensitive material
Made >> (Preparation of sample 11) High-density polyethylene is added on one side
One surface contains 15% by mass of anatase type titanium oxide.
Laminated molten polyethylene containing a large amount of dispersed
Mass is 115g / m²On a paper-pulp reflective support of
EM-B1, EM-G1, EM-R1 and EM-IR1
Each of the emulsions described in Tables 2 and 3 was used to oxidize each layer.
It is applied on the side of the polyethylene layer containing tongue
Gelatin 7.2g / m on the side ², Silica matting agent 0.6
5 g / m²A sample 11 coated with was prepared. Hardener
As a result, H-1 and H-2 were added. For coating aid and dispersion
As the auxiliary agent, surfactants SU-1, SU-2, SU-
3 was added.

SU-1: sulfosuccinate di (2-ethylhexyl) ester sodium SU-2: sulfosuccinate di (2,2,3,3,4,4,4)
5,5-Octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalene sulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: tetrakis (vinyl) The amount of the compound applied to each layer of sulfonylmethyl) methane was expressed in g / m ² . The addition amount of the silver halide emulsion was converted to silver and displayed.

[0147]

[Table 2]

[0148]

[Table 3]

Details of each of the other additives used in the preparation of the above-mentioned sample 11 are shown below. SO-1: trioctylphosphine oxide SO-2: di-i-decyl phthalate SO-3: p-t-octylphenol SO-4: tricresyl phosphate HQ-1: 2,5-di (t-butyl) hydroquinone HQ-2: 2,5-bis [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5-di-sec-tetra Mixture of decylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone in a mass ratio of 1: 1: 2 ST-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-3: N-benzyl Adenine ST-4: 2-Mercaptobenzothiazole LA-1: Copolymer of acrylic acid and methacrylic acid

[0150]

[Chemical 7]

[0151]

[Chemical 8]

[0152]

[Chemical 9]

In the preparation of the sample 11, the color analyzer 607 was applied when the first to fourth layers were coated.
The surface reflection density at 730 nm was measured using a mold (manufactured by Hitachi). Then, the same sample is subjected to the development processing described above,
Similarly, the surface reflection density at 730 nm was measured, and the obtained results are shown in Table 4.

(Preparation of Samples 12 to 30) In Sample 11 prepared above, the addition amount of the anti-irradiation dye (AI-4) in the fourth and second layers and the addition amount of black colloidal silver in the first layer were changed. Samples 12 to 30 were produced in the same manner except that the addition amount shown in Table 4 was changed.

<< Exposure and development treatment of silver halide color photographic light-sensitive material >> [Exposure condition] Each of the above-prepared samples was cut into a width of 670 mm and a length of 45 m, and wound around a core so that the image-formed surface was exposed. It was processed into a roll and stored in a bright room type cartridge.

Each of the roll-shaped samples produced as described above was exposed under the following exposure condition-Y by bringing the yellow plate of the original halftone dots into close contact with the sample. Then, the magenta plate was brought into close contact with the sample and exposed under the exposure condition-M shown below. Then, the cyan plate was brought into close contact with the sample and exposed under the exposure condition-C shown below. Next, the black plate was brought into close contact with the sample and exposed under the exposure condition-K shown below. In the original halftone dot original used above, an image having 175 lines / inch and a halftone dot area of 50% (hereinafter, also referred to as a midpoint) is incorporated in each of the yellow plate, the magenta plate, the cyan plate, and the black plate. Therefore, it is possible to evaluate what halftone dot area the image of the 50% halftone dot portion is reproduced. Separately, it has an image portion in which the dot reproducibility and the dot quality can be evaluated by changing the dot area ratio of each plate between 0 and 100%. The inch referred to in the present invention means 2.54 cm.

(Exposure condition-Y) An infrared light source was used for each sample, a filter that transmits infrared light (LEE filters 026 and 363 were overlapped and used), and a 50% yellow mesh after development processing was used. Exposure was performed by adjusting the exposure amount with an ND filter so that the halftone dot area of the dot original portion was 64%. The exposure time is 0.1 seconds.

(Exposure condition-M) Each of the light-sensitive materials was provided with a blue filter (Ratten No. 47B) as a white light source, and the halftone dot area of the magenta 50% halftone dot original portion after development was 64%. Thus, the exposure amount was adjusted with the ND filter to perform the exposure. The exposure time is 0.1 seconds.

(Exposure condition-C) Each of the light-sensitive materials was provided with a white light source, a red filter (Ratten No. 26), and after development, 50% of cyan halftone dot area of the original portion was 6
Exposure was carried out by adjusting the exposure amount with an ND filter so that it would be 4%. The exposure time is 0.1 seconds.

(Exposure condition-K) Each of the light-sensitive materials was subjected to a white light source with a green filter (Ratten No. 58), and further, after development processing, the halftone dot area of the cyan 50% halftone original portion was 6%.
Exposure was carried out by adjusting the exposure amount with an ND filter so that it would be 4%. The exposure time is 0.1 seconds.

As the infrared light source used in the exposure condition -Y, an infrared fluorescent lamp that emits infrared light was used. A daylight fluorescent lamp was used as the white light source used for exposure conditions M, C, and K. In each of the above exposure conditions, at the time of exposure, each sample was fixed on the exposure table by a vacuum suction adhesion method,
After the original films were brought into close contact with each other, scanning exposure was carried out using a corresponding light source.

[Development Processing] Development processing was carried out under the following processing condition-1. However, in the fogging exposure, the surface of the sample was uniformly exposed on the entire surface while being immersed in the developing solution and passed through a developing solution tank having a thickness of 3 mm. The developing treatment was carried out after continuous treatment with each sample until the total amount of the developing solution at the start of development and the developing replenisher solution replenished under the conditions described below became 3 times the developing tank volume. The development process was performed using both the developer.

(Processing Step-1) Processing Step Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds Development 37 ° C 95 seconds Bleaching fixing 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Drying 60-85 ° C. 40 seconds (color developer composition) benzyl alcohol 15.0 ml cerium 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 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.1 g Hydroxylamine sulfate 5.0 g Diethylenetriaminepentaacetic acid pentasodium 2.0 g 4-Amino-N-ethyl-N- (β- Hydroxyethyl) aniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfone The total volume of 1000ml by adding acid derivative) 1.0 g Potassium hydroxide 2.0g diethylene 15.0ml water, adjusted to PH10.15.

(Composition of bleach-fixing solution) Diethylenetriamine pentaacetate ferric ammonium 90.0 g Diethylenetriamine pentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1 , 2,4-Triazole 0.15 g The pH is adjusted to 7.1 with potassium carbonate or glacial acetic acid, and water is added to bring the total amount to 1 liter.

(Stabilizing solution composition) o-phenylphenol 0.3 g potassium sulfite (50% aqueous solution) 12.0 ml ethylene glycol 10.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g Zinc sulfate 7-hydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Optical brightener (4,4′-diaminostilbene disulfonic acid derivative) 2.0 g Water In addition, the total amount is adjusted to 1 liter, and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

The stabilization treatment was a countercurrent system having a three-tank construction. Below, the prescription of each replenisher when performing a running process is shown.

(Color development replenisher) benzyl alcohol 18.5 ml cerium sulfate 0.015 g ethylene glycol 10.0 ml potassium sulfite 2.5 g potassium bromide 0.3 g sodium chloride 0.2 g potassium carbonate 25.0 g 4-hydroxy -6-Methyl-1,3,3a, 7-tetrazaindene 0.1 g Hydroxylamine sulfate 5.0 g Diethylenetriamine pentaacetic acid pentasodium 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline Sulfate 5.4 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Water is added to adjust the total volume to 1 liter and the pH is adjusted to 10.35.

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

(Stabilizing Solution Replenishing Solution) Same as the above stabilizing solution.

The replenishing amount of the developing replenisher, the bleach-fixing solution and the stabilizing solution was 320 ml per 1 m ^{2 of} the light-sensitive material.

The development processing is performed by Konsens manufactured by Konica Corporation.
An automatic processor of us670 was used. << Evaluation of silver halide color photographic light-sensitive material >> The following evaluations were performed on the developed samples obtained as described above.

(Evaluation of Small Spot Reproducibility of Yellow Image) The small spot reproducibility of yellow was evaluated for the sample which was processed using the development start solution and the developer after continuous processing. Evaluation is 1 for each halftone dot when the halftone dot area is 64%.
Percentage of dots that can be distinguished by visual evaluation using a 0x magnifier
I asked.

(Measurement of Color Difference ΔE of White Background Part) The color difference of the white background part of the obtained image when the halftone dot area of the midpoint is 64% was measured according to the method described below.

For the color difference measurement, the white background portion (unexposed portion) was measured with a spectrocolorimeter CM-2022 manufactured by Minolta Co., Ltd. using a geometric condition d-0 of illumination and light reception and a xenon pulse light source, and 2 °. L ^* , a ^* , b ^{* at} field of view, auxiliary standard light D50
Value was measured at 10 points and the average value was calculated, and the color difference Δ of the sample processed using the development start solution and the developer after continuous processing
E was calculated by the following formula.

ΔE = (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 Here, ΔL ^* , Δa ^* , and Δb ^* represent the difference between the two conditions.

Table 4 shows the results obtained as described above.

[0177]

[Table 4]

As is apparent from Table 4, 730 from the support to the yellow image forming layer before the development according to the present invention.
The sample having a surface reflection density of 1.1 or more at nm and a surface reflectance of 0.1 or less at 730 nm after development is excellent in small point reproducibility before and after continuous processing and reproducibility stability as compared with Comparative Example. Moreover, it can be seen that there is little change in the color tone of the white background. In addition, the small point reproducibility evaluation was performed on the magenta image, the cyan image, and the black image in the same manner as above, and as a result, similar to the evaluation result of the yellow image, the small point reproducibility of the sample according to the present invention was evaluated. It was possible to confirm the excellent effect on the reproduction stability.

Example 2 In the preparation of Sample 11 described in Example 1, the infrared-sensitive emulsion (EM-IR1) used in the third layer was replaced with the following infrared-sensitive emulsions, and the first infrared-sensitive emulsion was further used. In the same manner, except that the composition of the layers, the second layer, and the fourth layer are changed to the contents described below.
Samples 40 to 51 were produced.

(Preparation of infrared-sensitive emulsion) In the preparation of the infrared-sensitive emulsion EM-IR1 described in Example 1, instead of the emulsion EM-P2 used, a metal compound of Infrared photosensitive Emulsion E was prepared in the same manner as above except that the type and the amount added were changed as shown in Table 5.
M-IR2-EM-IR12 were prepared and used for the third layer of Samples 41-51 as described in Table 5. Sample 40
Used the infrared-sensitive emulsion EM-IR1 prepared in Example 1.

(Fourth layer: intermediate layer) Coating amount (g / m ² ) Gelatin 0.70 Anti-staining agent (HQ-2) 0.04 Anti-staining agent (HQ-3) 0.02 High boiling point solvent (SO -2) 0.01 Anti-irradiation dye (AI-1) 0.03 Anti-irradiation dye (AI-2) 0.03 (Second layer: intermediate layer) Gelatin 0.40 Anti-staining agent (HQ-2) 0.01 Anti-staining agent (HQ-3) 0.005 High boiling point solvent (SO-2) 0.003 Anti-irradiation dye (AI-4) 0.07 Fluorescent brightener solid particles (F-10) 1. 40 (First layer: antihalation layer) Gelatin 0.60 Latex (LA-1) 0.12 Black colloidal silver 0.04 Polyvinylpyrrolidone 0.10 Titanium oxide 1.00 Sample prepared as above Regarding 0 to 51, after performing exposure and development processing according to the method described in Example 1, the small point reproducibility of the yellow image and the color difference ΔE of the white background portion were measured by the same method, and the obtained results were obtained. It shows in Table 5.

[0182]

[Table 5]

As is clear from Table 5, the sample of the present invention containing a metal ion or a metal complex ion having an electron trap depth of 0.35 eV or more was superior to the comparative example in small point reproducibility and continuously treated. It can be seen that the fluctuation of the white background is small.
In addition, the small point reproducibility evaluation was performed on the magenta image, the cyan image, and the black image in the same manner as above, and as a result, similar to the evaluation result of the yellow image, the small point reproducibility of the sample according to the present invention was evaluated. It was possible to confirm the excellent effect on the reproduction stability.

Example 3 In the sample 41 produced in Example 2, the second layer and the fourth layer were used.
Samples 61 to 69 were prepared in the same manner except that equimolar amounts of the compounds shown in Table 6 were used instead of the high boiling point solvent (SO-2) used in each intermediate layer of the layers, and described in Example 1. After exposure and development according to the above method, the dot reproducibility of the yellow image and the color difference ΔE of the white background portion were measured by the same method, and the obtained results are shown in Table 6.

SO-4 shown in Table 6 is dibutyl phthalate.

[0186]

[Table 6]

As is clear from Table 6, the sample of the present invention using the compound represented by the general formula (1) and the hydroquinone derivative in the intermediate layer is excellent in the small dot reproducibility of the yellow image and is continuously processed. It can be seen that the fluctuation of the white background in is small. In addition, the small point reproducibility evaluation was performed on the magenta image, the cyan image, and the black image in the same manner as above, and as a result, similar to the evaluation result of the yellow image, the small point reproducibility of the sample according to the present invention was evaluated. It was possible to confirm the excellent effect on the reproduction stability.

Example 4 In the sample 41 prepared in Example 2, each photosensitive layer was replaced by
As shown in Table 7, Samples 81 to 87 were prepared in the same manner except that the third layer, the fifth layer, the seventh layer, and the eleventh layer were applied in different arrangement orders, respectively, and described in Example 1. After exposure and development according to the method of 1., the small point reproducibility of the yellow image and the color difference ΔE of the white background are measured by the same method,
The results obtained are shown in Table 7.

[0189]

[Table 7]

As is clear from Table 7, the sample having the layer arrangement defined in claim 4 is excellent in the small dot reproducibility of the yellow image and has a small white background variation during continuous processing. In addition, the small point reproducibility evaluation was performed on the magenta image, the cyan image, and the black image in the same manner as above, and as a result, similar to the evaluation result of the yellow image, the small point reproducibility of the sample according to the present invention was evaluated. It was possible to confirm the excellent effect on the reproduction stability.

[0191]

INDUSTRIAL APPLICABILITY The present invention provides an image forming method of a silver halide color photographic light-sensitive material which is excellent in small dot reproducibility and white background variation even when continuous processing is carried out when a proof color image (color proof) is produced. Could be provided.

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Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer on a support, up to the yellow image forming layer on the support. An image forming method for a silver halide color photographic light-sensitive material, wherein the surface reflection density at 730 nm when formed is 1.1 or more and the surface reflection density after development is 0.1 or less. 2. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer on a support, and the halogenation contained in the yellow image forming layer. An image forming method for a silver halide color photographic light-sensitive material, characterized in that the silver particles contain therein a metal ion or a metal complex ion having an electron trap depth of 0.35 eV or more. 3. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer, cyan image forming layer and an intermediate layer on a support, wherein the intermediate layer contains a hydroquinone derivative. A method of forming an image of a silver halide color photographic light-sensitive material, which comprises a compound represented by the following general formula (1). [Chemical 1] [In the formula, R ₁ , R ₂ and R ₃ each represent a substituent, and p, q
And r represents 0 or 1. However, p, q, and r are not all 1. ] 4. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer on a support, wherein the yellow image forming layer is infrared sensitive. Containing a photosensitive silver halide emulsion, located closer to the support than the blue-sensitive silver halide emulsion layer, and located above the green-sensitive silver halide emulsion layer or the red-sensitive silver halide emulsion layer. An image forming method for a silver halide color photographic light-sensitive material, comprising: