JP3219206B2 - Color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a color image having excellent color reproducibility and gradation reproducibility on a silver halide photographic light-sensitive material having a reflective support from soft information recorded on a magnetic medium or the like. The present invention relates to an image forming method to be formed.

[0002]

BACKGROUND OF THE INVENTION Today in the field of electronics, C
2. Description of the Related Art The remarkable progress of image pickup devices such as CDs and magnetic recording media has made it possible to take pictures with the same ease as conventional pictures using silver halide, and immediately transfer them to a television to enjoy them. In the field of printing and plate making, thanks to advances in scanners and image processing equipment, after reading the original image with a scanner, you can easily edit, correct, change contrast, enlarge and reduce the size, etc. while looking at the color display. You can now do it. As described above, recording and processing of an image as an electric signal is permeating not only in the industrial field but also in the general society.

[0003] However, simply displaying an image on a television screen is still not satisfactory, and an image recorded on paper is required, and various methods such as a thermal transfer method, an ink jet method, and an electrophotographic method are used. Has been put to practical use. Even in these fields, the rich color reproducibility of silver halide photographic light-sensitive materials is outstanding compared to other methods, and helium-neon, argon ion, helium-
By performing scanning exposure on a silver halide photographic material using a gas laser such as cadmium as a light source, a color image having excellent color reproducibility can be formed. However, an image formed by using a conventionally known silver halide photographic light-sensitive material as it is as a light-sensitive material for scanning exposure has a drawback that color turbidity (particularly, a yellow color image) occurs due to a problem of high illumination reciprocity failure. This is described in, for example, JP-A-62-35352. Japanese Patent Application Laid-Open No. 62-35352 discloses that an image with less color turbidity can be formed by setting the silver bromide content of the silver halide in the silver halide emulsion layer to 0 to 65 mol%. Have been. This technique prevents color turbidity, improves color purity, and improves the color reproducibility of the formed image.

Many factors affect the color reproducibility of an image formed by exposure from a color negative film, such as the spectral sensitivity of the color negative film, the layering effect, and the spectral absorption of the dye. Therefore, a color photographic paper required to form an image with good color reproducibility from a color negative film has characteristics in accordance with various characteristics of the color negative film.
For this reason, when these conventional color printing papers are used in the digital color image forming method, there is a problem that high-saturation colors, particularly high-saturation red, cannot be sufficiently reproduced. Furthermore, these conventional photographic papers have a problem that the high-saturation red gradation is lost.
For example, JP-A-61-91657 and JP-A-62-67537.
Nos., 62-258453 and 63-236034. For example, JP-A-62-258453
No. 1 discloses that reducing unwanted absorption of the magenta imaging dye causes the problem of loss of high chroma red tones. Also, as described in JP-A-61-91657.
No. 62-67537, No. 62-258453,
JP-A-63-236034 specifically describes methods for preventing the disappearance of high-saturation red gradation. In those methods, although the improvement of red gradation reproduction is seen, the high-saturation red gradation itself is prevented. It has the disadvantage that the hue changes and the lightness also decreases.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a digital color image forming method for forming a color image having excellent color reproducibility and gradation reproducibility.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a digital / analysis method in which a silver halide photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a magenta coupler and a cyan coupler on a reflective support is exposed and developed. In the color image forming method, when the image density of the yellow color patch obtained by the color image forming method is 2.0, the chromaticity is 86 degrees or more and 90 degrees or more in the CIE 1976 L ^* a ^* b ^* color space. And the chromaticity at the time when the image density of the magenta color patch is 2.0 is C
When the metric hue angle is 340 degrees or more and 355 degrees or less in the IE 1976L ^* a ^* b ^* color space, the metric chroma is 70.
This can be achieved by a color image forming method characterized as described above.

In the case of a digital color image forming method by scanning exposure in which the exposure amount per pixel is 10 ^-4 seconds or less,
The achievement of the above objects is achieved by the Group VIII metals, Group II metals,
The use of a silver halide photographic material having at least one silver halide emulsion layer containing at least one of compounds having lead, rhenium, molybdenum, tungsten, and chromium makes it more excellent.

[0008] Further, the above object is achieved by both the exposure to the silver halide emulsion layer containing the yellow coupler and the exposure to the silver halide emulsion layer containing the magenta coupler, which are exposures to give a high-density image, and When the exposure amount for the coupler-containing silver halide emulsion layer is an exposure amount that gives a cyan image having a density of 0.5 or less, when the exposure for the cyan coupler-containing silver halide emulsion layer is not satisfied, It is excellent when the exposure is calculated so as to form an image having a higher contrast than the image formed in the silver halide emulsion layer containing a cyan coupler.

Hereinafter, the present invention will be described in detail.

In the present invention, the metric hue angle is
After a photographic component layer including a coupler-containing silver halide emulsion layer is coated on a reflective support having a smooth surface, the color patch is exposed by exposing it to light having an appropriate spectral composition and developed to form a color patch. It can be obtained by measuring its spectral absorption. "Yellow color pack
When the image density of the image becomes 2.0 "
The image density of the yellow color patch is 2.
0 means the part where “Magenta color patch image density
"When the degree reaches 2.0"
Part where the image density becomes 2.0 in the colored patch
Say a minute. Spectral absorption is measured according to JIS Z-8722 (1.
982), and measured under the condition c of the geometrical conditions of illumination and light reception, and also in JIS Z-8722 (1982).
The tristimulus values X, Y, and Z are determined by the method described in
The value of each L ^* a ^* b ^* is determined by the method described in Z-8729 (1980). Metric hue angle is CIE
1976 L ^* a ^* b ^* in the a ^* b ^* plane in the color space a ^* of a ^* axis Yes defines a positive axial portion as 0 degree refers to the angle from the axis. At that time, if a ^* > 0 and b ^* > 0,
The metric hue angle is in the range of 0-90 degrees and a ^* <
90-180 degrees when 0, b ^* > 0, a ^* <0, b ^* <
In the case of 0, it is in the range of 180 to 270 degrees, in the case of a ^* > 0, and in the case of b ^* <0, it is in the range of 270 to 360 degrees. The metric chroma is defined by the distance between the L ^* axis in CIE1976L ^* a ^* b ^* color space. Details of these are described in, for example, Yoshinobu Naya: Industrial Colorology, pp. 106-107, Asakura Shoten (1989) and the like. The image density has the status A spectral condition specified in JIS K 7653-1988, and the image density is JIS K 7654-1.
This is obtained by measuring the density of a color patch using a densitometer that satisfies the geometric conditions specified in 990.

In the present invention, the chromaticity when the image density of the yellow color patch becomes 2.0 is CIE 197.
6 In the L ^* a ^* b ^* color space, the metric hue angle is 86 degrees or more and 90 degrees or less, the metric chroma is 85 or more, and
It is required that the chromaticity when the image density of the magenta color patch becomes 2.0 is a metric hue angle of 340 degrees or more and 355 degrees or less and a metric chroma of 70 or more in the CIE 1976 L ^* a ^* b ^* color space. It is.

The metric hue angle and metric chroma of yellow and magenta images are determined primarily by the structure of the yellow and magenta image dyes. Therefore, whether or not the above metric hue angle and metric chroma can be obtained is most influenced by the structures of the yellow coupler, the magenta coupler and the color developing agent, particularly the structures of the yellow coupler and the magenta coupler. However, besides this, it is used for dispersing couplers and additives that have a relatively small effect but have the ability to shift the spectral absorption of image dyes to longer or shorter wavelengths due to the formation of intermolecular hydrogen bonds. Kind and amount of high boiling organic solvent and polymer, quantitative ratio of coupler to high boiling organic solvent,
The amount of the dispersion of the coupler and the like are affected.

In the present invention, the chromaticity when the image density of the yellow color patch becomes 2.0 is CIE 197.
In the 6 L ^* a ^* b ^* color space, a requirement that the metric hue angle is 86 degrees or more and 90 degrees or less and the metric chroma is 85 or more (hereinafter referred to as requirement Y of the present invention) is required. More preferably, the chromaticity when the image density becomes 2.0 satisfies the requirement that the metric hue angle is 87 degrees or more and 89 degrees or less and the metric chroma is 85 or more in the CIE 1976 L ^* a ^* b ^* color space. Preferred examples of the yellow coupler capable of forming a yellow image satisfying the requirement Y of the present invention include a compound represented by the following formula (Y). General formula (Y)

[0014]

Embedded image In the formula, R _Y1 represents an alkoxy group, and R _Y2 represents —NHCOR
_Y3 SO ₂ R _Y4 , COOR _Y4 , -NHCOR _Y4 , -COO
_{R Y3 COOR Y4, -N (R} Y5) SO 2 R Y4 or -SO ₂
N (R _Y5 ) R _Y4 . R _Y3 represents an alkylene group;
_Y4 represents a diffusion-resistant group; R _Y5 represents a hydrogen atom, an alkyl group or an aralkyl group; and Z _Y represents a coupling-off group.

Preferred yellow couplers which can be used in the present invention to exhibit the effects thereof include the following YC-1 to YC-
9, but is not limited thereto.

[0016]

Embedded image

[0017]

Embedded image

Even if a yellow coupler which cannot form a yellow image which satisfies the requirement Y of the present invention by itself is used, if the requirement Y of the present invention can be satisfied by using it in combination with another coupler, the present invention Can be used for the silver halide photographic light-sensitive material.

In the present invention, the chromaticity when the image density of the magenta color patch becomes 2.0 is CIE 197.
In the 6 L ^* a ^* b ^* color space, a requirement that the metric hue angle is 340 degrees or more and 355 degrees or less and the metric chroma is 70 or more (hereinafter referred to as requirement M of the present invention) is required. More preferably, the chromaticity when the image density becomes 2.0 satisfies the requirement that the metric hue angle is 345 degrees or more and 350 degrees or less and the metric chroma is 70 or more in the CIE 1976 L ^* a ^* b ^* color space.

The following are specific examples of magenta couplers capable of forming a magenta image satisfying the requirement M of the present invention, but the present invention is not limited thereto.

[0021]

Embedded image

Even if a magenta coupler that cannot form a magenta image that satisfies the requirement M of the present invention by itself is used, if the requirement M of the present invention can be satisfied by using it in combination with another coupler, the present invention Can be used for the silver halide photographic light-sensitive material.

When an oil-in-water emulsion dispersion method is used to add the coupler according to the present invention to a silver halide photographic light-sensitive material, it is usually necessary to use a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or water-soluble organic solvent is used in combination and dissolved, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of the high boiling point organic solvent which can be used for dissolving and dispersing the coupler include (1) dioctyl phthalate (2) dinonyl phthalate (3) diisododecyl phthalate (4) dicyclohexyl phthalate (5) tricresyl phosphate (6) trihexyl phosphate (7) tri (2-ethylhexyl) phosphate (8) diethyl lauramide (9) dinonylphenol (10) decalin (11) 1,4-bis (2-ethylhexylcarbonyloxymethyl) cyclohexane and the like I can give it.

The weight ratio of the coupler to the high boiling organic solvent is such that the high boiling organic solvent is
Is preferably used, and more preferably 0.2 to 1. A higher ratio of the high boiling point organic solvent makes it easier to obtain preferable spectral absorption, but is disadvantageous in terms of stability of the silver halide light-sensitive material and resistance to physical damage, and should be determined in consideration of both. It is.

In place of the method using a high-boiling organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer compound may be dissolved in a low-boiling and / or water-soluble organic solvent, if necessary, and a gelatin aqueous solution or the like may be used. A method of emulsifying and dispersing by using various kinds of dispersing means using a surfactant in a hydrophilic binder can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include [PO-1] poly (Nt-butylacrylamide) and [PO-2] Nt-butylacrylamide-methyl methacrylate copolymer (60:40). [PO-3] Polybutyl methacrylate [PO-4] Methyl methacrylate-styrene copolymer (90:10) [PO-5] Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) ) [PO-6] ω-methoxypolyethylene glycol acrylate (additional mole number n = 9) -Nt-butylacrylamide copolymer (25:75) [PO-7] 1,4-butanediol-adipate polyester [PO-8] polypropiolactam and the like. The numerical value in parentheses of the copolymer indicates the weight ratio of the monomer.

The following compounds can be used for shifting the absorption wavelength of the coloring dye.

[0027]

Embedded image In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 × 10 ^{−3 to} 5 mol, more preferably 1 × 10 ⁻³ mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

As the cyan coupler used in the silver halide photographic light-sensitive material according to the present invention, various conventionally known couplers can be used. By appropriately selecting the cyan coupler, excellent color reproducibility can be obtained. You can get an image. As specific examples of the cyan coupler used in the silver halide photographic light-sensitive material according to the present invention, the following CC-
1 to CC-12.

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide and silver chloroiodobromide. May be.

The silver halide emulsion used in combination with the yellow and magenta couplers according to the present invention is required to have a sufficient sensitivity and a sufficient maximum density. From this point, the silver halide emulsion according to the present invention includes iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, etc.
It is preferable to contain a Group II metal, a Group II transition metal such as cadmium, zinc, and mercury, and a heavy metal compound such as lead, rhenium, molybdenum, tungsten, and chromium. Among them, transition metal compounds of iron, iridium, platinum, ruthenium, and osmium are preferred.

In particular, in the case of a digital color image forming method by scanning exposure, it is preferable to include a transition metal compound of iron, iridium, platinum, ruthenium and osmium, and the effect of the present invention is high.

These heavy metal compounds can be added to a silver halide emulsion, for example, in the form of a salt or a complex. Above all, it is preferable to add it to the emulsion in the form of a complex, since it can be easily incorporated into the silver halide emulsion and the effect of the present invention is further increased.

When a heavy metal forms a complex, its ligands include stannate ion, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. Can be mentioned. Among them, stannate ion, thiocyanate ion, cyanate ion, halogenated stannate ion and the like are preferable.

The heavy metal compounds used in the silver halide emulsion according to the present invention are shown below.

(1) FeCl ₂ , (2) FeCl ₃ ,
(3) (NH ₄ ) Fe (SO ₄ ) ₂ , (4) K ₃ [Fe
(CN) ₆ ], (5) K ₄ [Fe (CN) ₆ ], (6)
K ₂ [IrCl ₆ ], (7) K ₃ [IrCl ₆ ],
(8) K ₂ [PtCl ₆ ], (9) K ₂ [Pt (SC
N) ₄ ], (10) K ₂ [NiCl ₄ ], (11) K ₂
[PdCl ₆ ], (12) K ₃ [RhCl ₆ ], (1
3) CdCl ₂ , (14) ZnCl ₂ , (15) K
₄ [IrBr (SnBr ₃ ) ₅ ], (16) K ₂ [M
o (CO) ₄ (CNO) ₂ ], (17) K ₃ [Re (C
NO) ₆ ], (18) K ₃ [Mo (OCN) ₆ ], (1
9) K ₄ [Fe (CNO) ₆ ], (20) K ₂ [W (C
O) ₄ (CNO) ₂ ], (21) K ₂ [Cr (CO) ₄
(CNO) ₂ ], (22) K ₄ [Ru (CNO) ₆ ],
(23) K ₂ [Ni (CN) ₄ ], (24) PbC
l ₂ , (25) K ₃ [Co (NH ₃ ) ₆ ], (26) K
₅ [Co ₂ (CNO) ₁₁ ], (27) K ₃ [Re (CN
O) ₆ ], (28) K ₄ [Os (SnCl ₃ ) ₆ ],
(29) K ₄ [Ru (SnCl ₃ ) ₆ ], (30) K ₄
[Os (CNO) ₆ ], (31) K ₂ [Cd (CNO)
₄ ], (32) K ₂ [Pt (CNO) ₄ ], (33) K
₃ [IrBr ₆ ]

In order for the heavy metal compound to be contained in the silver halide emulsion according to the present invention, the heavy metal compound of the present invention is formed before forming silver halide grains, during formation of silver halide grains, and during formation of silver halide grains. What is necessary is just to add in the arbitrary places of each process during the subsequent physical ripening. For this purpose, for example, the heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, it may be dissolved together with the halide salt and added continuously during the grain formation step.

When the heavy metal compound of the present invention is added to a silver halide emulsion, the amount is 10 ^-9 per mol of silver halide.
It is preferably at least molar, more preferably from 10 ^-9 mol to 10 ^-2 mol, particularly preferably 10 ^-8 mol to 10 ^-3 mol.

The halogenated emulsion used in the present invention is chemically sensitized by a conventional method.

The silver halide photographic light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. . Among them, a halogenated emulsion contained in at least one layer having a maximum value of spectral sensitivity on a longer wavelength side than 720 nm can be preferably used. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes. In the silver halide photographic light-sensitive material according to the present invention, the combination of each silver halide emulsion and coupler is not particularly limited.

Preferred specific compounds of the infrared sensitizing dye used in the present invention are shown below.

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image The red-sensitive and infrared-sensitive sensitizing dyes used in the present invention can be used in combination with the following compounds as supersensitizers.

[0048]

Embedded image

[0049]

Embedded image

As the exposure method in the digital color image forming method of the present invention, a scanning exposure method using a laser, a light emitting diode, or the like, a CRT (cathode ray tube) exposure method, a liquid crystal exposure method, or the like can be used.

In the exposure apparatus of the digital color image forming method of the present invention, the apparatus for scanning and exposing using a laser includes three exposures corresponding to the photosensitive areas of three emulsions combined with a yellow coupler, a magenta coupler and a cyan coupler. It has a light source. This light source can be selected according to its wavelength, and a gas laser such as helium / cadmium, argon ion, helium / neon, or a semiconductor laser can be used in combination.

In particular, it is preferable to use a semiconductor laser in consideration of miniaturization and cost reduction of the device. Any semiconductor laser may be used as long as it has a sufficient intensity at a wavelength of 720 nm or more, such as gallium / arsenic / phosphorus, aluminum / gallium / arsenic, indium / gallium / arsenic / phosphorus, and aluminum / phosphorus. Gallium, arsenic, antimony and the like can be given. Among them, 75
Semiconductor lasers having wavelengths of 0, 780, 810, 830, and 880 nm are advantageously used in terms of light intensity, handling of silver halide photosensitive materials, and the like.

The shape of the laser beam used for exposure is not particularly limited, and may be circular or elliptical. The size of the beam is not particularly limited, but the smaller the size of the beam is, the higher the image quality can be obtained. As a laser printer device considered to be applicable to such a system, for example, Japanese Patent Application Laid-Open No. 55-407
No. 1, JP-A-59-11062, JP-A-63-197
947, JP-A-2-74942, JP-A-2-236
No. 538, No. 56-14963, No. 56-4
No. 0822, European Patent 77410, IEICE Technical Report No. 80, No. 244, and Movie Television Technical Journal 1
984/6 (382), pages 34 to 36, and the like.

In the exposure method of the digital color image forming method of the present invention, in the case of exposure by CRT, three light emitting phosphors corresponding to the photosensitive areas of three emulsions combined with a yellow coupler, a magenta coupler and a cyan coupler are used. CRT can be used. The light emitting phosphor can be manufactured by a normal manufacturing method, for example, by using a manufacturing method described in JP-A-61-296647. The light emitting phosphor that emits light in the blue, green, red, yellow, orange, violet or infrared region can be used.

Exposure to the silver halide emulsion layer containing the yellow coupler, the silver halide emulsion layer containing the magenta coupler, and the silver halide emulsion layer containing the cyan coupler depends on data for controlling the exposure amount of each layer recorded on a magnetic recording medium or the like. The exposure is controlled by the signal output based on the exposure. In this case, the output image can be changed to a desired one by processing the output signal based on the data.

A signal for controlling the exposure amount applied to the silver halide emulsion layer containing the yellow coupler and the signal for controlling the exposure amount applied to the silver halide emulsion layer containing the magenta coupler are both signals for providing a high density yellow image and a high density magenta image. When the condition that the signal for controlling the exposure amount applied to the cyan coupler-containing silver halide emulsion layer is a signal that provides a cyan image having a density of 0.5 or less is satisfied, the exposure amount to be applied to the cyan coupler-containing silver halide emulsion layer The arithmetic processing of the signal for controlling the exposure is performed to control the exposure to give a higher contrast than the contrast of the cyan image formed in the cyan coupler-containing silver halide emulsion layer when the above conditions are not satisfied. Can be improved.

In the present invention, the yellow coupler containing yellow coupler
Exposure dose and magenta coupler for silver logenide emulsion layer
Exposure to the silver halide emulsion layer containing
Exposure that gives an image and contains cyan coupler
When the exposure amount to the silver halide emulsion layer is 0.5 or less
The condition that the exposure amount gives a cyan image
Exposure of the coupler-containing silver halide emulsion layer
Line with the exposure calculated to form the
Is a requirement that determines the starting point for
It depends on what image is output. That is, the concentration of the yellow image and magenta image with which to start the operation processing a signal for controlling the exposure amount giving a cyan coupler-containing silver halide emulsion layer is determined by either output any image, high density, e.g. It can be 1.0 or more, or 1.5 or more.

The calculation of the signal for controlling the amount of exposure given to the cyan coupler-containing silver halide emulsion layer can be performed as analog or digital.

In the silver halide photographic material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used.

As the reflection support according to the present invention, any material may be used. Examples of the support include polyethylene-coated paper containing white pigment, baryta paper, vinyl chloride sheet, polypropylene containing white pigment, and polyethylene terephthalate support. Can be used. Among them, a support having on its surface a polyolefin resin layer containing a white pigment is preferable.

As the white pigment used in the reflection support according to the present invention, an inorganic and / or organic white pigment can be used, and preferably, an inorganic white pigment is used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion on the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material according to the present invention are aminophenol and p-phenylenediamine widely used in various color photographic processes. A system compound is used. In particular, aromatic primary amine color developing agents are preferably used. A known developer component compound can be added to the color developing solution in addition to the above-described color developing agent.

The silver halide photographic light-sensitive material according to the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or the water washing and the stabilization treatment may be used in combination. The development processing apparatus used for the development processing of the silver halide photographic light-sensitive material according to the present invention includes:
The roller transport type, which transports the photosensitive material between rollers disposed in the processing tank, or the endless belt type, which transports the photosensitive material fixed on a belt, may be used. To form
A system in which a processing solution is supplied to the processing tank and a photosensitive material is transported may be used.

[0066]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 A multilayer silver halide photographic light-sensitive material 101 having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. 26.7 g of a yellow coupler (Y-1),
Dye image stabilizer (ST-1) 10.0 g, Dye image stabilizer (ST-2) 6.67 g, Additive (HQ-1)
0.67 g and 6.67 g of high boiling point organic solvent (DNP)
Was dissolved in 60 ml of ethyl acetate, and this solution was dissolved in 10 ml of 9.5 ml of a 15% aqueous solution of a surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of an aqueous% gelatin solution using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (Em-B) (containing 8.68 g of silver) prepared under the following conditions.
Further, 6.7 ml of a 5% aqueous solution of an anti-irradiation dye AI-3 was added to prepare a coating solution for the first layer. 2nd to 7th layers
The layer coating solution was prepared in the same manner as the first layer coating solution. Also,
(H-1) was added to the second and fourth layers as a hardener, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

The layer structure is as shown in Tables 1 and 2.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

(Preparation of Blue-Sensitive Silver Halide Emulsion) The following (A) was added to 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C.
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 7.3, pH = 18 while controlling to 5.5
Co-added over 0 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 10 g of potassium bromide 1.0 g of water Add 600ml (Solution D) 300g Silver nitrate Add water 600ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle size of 0.85 μm, a coefficient of variation (S / R) = 0.07, and a silver chloride content. 99.5 mol% monodisperse cubic emulsion (EMP-
1) was obtained. Here, S represents the standard deviation of the particle diameter, and R represents the average particle diameter.

The emulsion (EMP-1) was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

(Preparation of Green-Sensitive Silver Halide Emulsion) (A
(EMP-1) except that the addition time of (Solution) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
Average particle size 0.43 μm, coefficient of variation (S / R) = 0.0
8. A monodisperse cubic emulsion (EMP-2) having a silver chloride content of 99.5 mol% was obtained. (EMP-2) was changed to a green sensitizing dye (GS-1), and the amount of each component was changed so that it could be optimally sensitized. Chemical ripening was performed at 55 ° C. for 120 minutes. Was subjected to chemical ripening in the same manner as in Em-B to obtain a green-sensitive silver halide emulsion (Em-G).

(Preparation of Red-Sensitive Silver Halide Emulsion) (A
(EMP-1) except that the addition time of (Solution) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
Average particle size 0.50 μm, coefficient of variation (S / R) = 0.0
8. A monodispersed cubic emulsion (EMP-3) having a silver chloride content of 99.5 mol% was obtained. Except that (EMP-3) was changed to a red-sensitive sensitizing dye (RS-1), and furthermore, the amount of each component was changed so as to be optimally sensitized, and chemical ripening was performed at 60 ° C. for 90 minutes. Was subjected to chemical ripening in the same manner as in Em-B to obtain a red-sensitive silver halide emulsion (Em-R).

[0082]

Embedded image

The silver halide photographic material was subjected to color separation scanning exposure using a scanning exposure apparatus described later, and then subjected to the following development processing to obtain a yellow color patch and a magenta color patch having a density of 2.0. The metric hue angles and metric chroma of these color patches were calculated according to the method described above. Table 3 shows the results.

[Color developing solution] Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 0 g ethylenediaminetetraacetic acid 1.0 g catechol-3,5-disulfonate disodium 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g fluorescent brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to make the total volume 1 liter, and the pH is adjusted to 10.10.

[Bleaching and Fixing Solution] Ethylenediaminetetraacetate ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to bring the total volume to 1 liter. PH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing Solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7 with sulfuric acid or potassium hydroxide. Adjust to .0.

Next, in the preparation of Sample 101, the yellow coupler (Y-1) and the magenta coupler (M-1) were prepared as shown in Table 3.
Samples 102 to 114 were prepared by changing as shown.

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

[Table 3]

For each of the samples 101 to 114, data obtained by digitally digitizing an image of a 4 × 5 inch color slide with a scanner at a size of 50 × 50 μm per pixel using a helium / cadmium laser as a blue light source was used. Approximately 442 nm), a helium-neon laser (about 544 nm) as a green light source, and a helium-neon laser (about 633 nm) as a red light source. Exposure at 0.6 m / sec. The exposure amount for the image data is determined independently from the blue, green, and red data of the image data. Next, development processing was performed in the above processing steps.

Printed images were obtained on the photosensitive materials of Samples 101 and 102 by the usual method from the color negative films photographed at the same time when the color slide image was created.
As 15, 116. The output image obtained in this way is
Presented to a human subject and asked to evaluate it sensuously from the viewpoint of the color reproducibility of the image. One point is given for poor ones, three points for ordinary ones, and five points for excellent ones. Was performed. The average value of the scores was obtained, and the print image was evaluated. Table 4 shows the results.

The following four scenes were used for evaluation. (1) Portrait of a woman (2) Group photo (3) Mountain landscape photo (4) Amusement park landscape photo

[0095]

[Table 4]

As described above, in all scenes, the combination of the present invention greatly improves the color reproducibility. Particularly, the effect of improving the color reproducibility in the scene (4) is remarkable because the scene (4) contains many high-saturation colors, and the combination of the present invention has high fidelity and high fidelity. It was concluded that this was due to the reproduction. In addition, Sample 1 of the present invention
02 is particularly effective in improving color reproduction. (Example 2) Images obtained by attaching the samples 101 to 114 used in Example 1 to a drum and photographing and recording color chips including high saturation blue, red, green, yellow, magenta, cyan and gray with a video camera. Was exposed and developed in the same manner as in Example 1. The light source for the exposure is a helium / cadmium laser (about 442 nm) as a blue light source, a helium / neon laser (about 544 nm) as a green light source, and a helium / neon laser (about 633 nm) as a red light source.
m) was prepared and the optical system was assembled. Beam diameter is about 8
Exposure was performed at 0 μm at a main scanning speed of 1.6 m / sec. The exposure amount for the image data is determined independently from the blue, green, and red data of the image data. Table 5 shows the results.

[0097]

[Table 5]

As can be seen from the above results, in the sample output by the method of the present invention, both red and yellow color patches have faithful hues and high chroma reproduction colors.
Further, it can be seen that the sample 202 has particularly high chroma and faithful hue color reproduction, and the effect of the invention is high. Example 3 A print image was evaluated in the same manner as in Example 1 except that the exposure method was changed to a CRT having a blue light-emitting phosphor, a green light-emitting phosphor, and a red light-emitting phosphor. It was confirmed that the image obtained by the method had a high effect of improving color reproduction. (Example 4) In the preparation of the blue-sensitive silver halide emulsion of Example 1, (solution C) was added in an amount of 1 per mol of the final silver halide.
A blue-sensitive silver halide emulsion was prepared in the same manner except that the above-mentioned heavy metal compounds (5) and (6) were added so as to be ^0-7 mol. Similarly, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion containing the exemplified heavy metal compounds (5) and (6) were prepared. Using these silver halide emulsions, an image was formed by scanning exposure in the same manner as in Example 1, and evaluation was made. As a result, it was confirmed that the effect of improving color reproduction was particularly high. (Example 5) In preparing samples 101 and 102 used in Example 1, the blue-sensitive emulsion (Em-B1) was replaced with the following infrared-sensitive emulsion 1 (Em-IR1), and a green-sensitive emulsion (Em-E1) was used.
-G) was replaced with the following infrared-sensitive emulsion 2 (Em-IR2), and dyes AI-3 and AI-1 were equimolar to dye AI-
Samples 301 and 302 were prepared in the same manner except that the sample was replaced with AI-5 and AI-5, respectively.

[0099]

Embedded image

(Preparation of infrared-sensitive silver halide emulsion 1)
The sample (EMP-2) was chemically ripened at 55 ° C. using the following compound to obtain an infrared-sensitive emulsion 1 (Em-
IR1) was obtained.

Sodium thiosulfate 1.5 mg / mole AgX Chloroauric acid 1.0 mg / mole AgX Stabilizer STAB-1 0.6 × 10 ⁻⁴ mol / mole AgX STAB at the time when optimum sensitometric performance is obtained
-1 was added to lower the temperature to stop the chemical ripening, but the infrared sensitizing dye IRS was added 3 minutes before the addition of STAB-1.
-7 was added for spectral sensitization. (Preparation of Infrared-sensitive Silver Halide Emulsion 2) The sample (EMP-2) was chemically ripened at 55 ° C. using the following compounds to obtain an infrared-sensitive emulsion 2 (Em-IR2). Was.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 0.6 × 10 ⁻⁴ mol / mol AgX STAB at the time when optimum sensitometric performance is obtained
-1 was added to lower the temperature to stop the chemical ripening, but the infrared sensitizing dye IRS was added 3 minutes before the addition of STAB-1.
-11 was added for spectral sensitization.

The exposure apparatus uses a helium / neon laser (about 633 nm) as a red light source and a gallium / aluminum / arsenic semiconductor laser (about 78 nm) as an infrared light source.
0, 830 nm), assembling the optical system,
Used for 1,302. The beam diameter is about 80 μm and 16
Exposure was performed at a light scanning speed of 0 m / sec. Using this apparatus, development processing after scanning exposure was performed in the same manner as in Example 2, and four scenes were evaluated in the same manner as in Example 2. Table 6 shows the results.

[0104]

[Table 6]

As described above, even when infrared rays are used for scanning exposure, an image having excellent color reproducibility is formed in the same manner as when an image is formed by scanning exposure with green and red visible light. I understand. (Example 6) In Example 2, when exposure with visible light of blue and green was performed at an exposure amount at which the yellow image density was 1.6 or more and the magenta image density was 1.6 or more, Exposure with visible light was calculated and provided so that the exposure amount between the lowest density and the density of the cyan image was 1.5 times the contrast between the other cases. Samples 101 to 11 of Example 1
Samples No. 4 were exposed and developed to be Samples 401 to 414, respectively. In the method for producing sample 101 of Example 1, 5 mol% of cyan coupler C- based on the magenta coupler of the third layer was used.
3 was added, and the amount of the cyan coupler was reduced from the amount of the cyan coupler of the fifth layer. Regarding these samples, in order to see the high chroma red discrimination for the scene (1) in Example 2, the discrimination of the stitches of the sweater is excellent (3 points), normal (2 points) and inferior ( (One point). Further, the color reproducibility of the obtained image was evaluated in five steps in the same manner as in Example 1. Table 7 shows the results.

[0106]

[Table 7] When the exposure with the red light is performed as described above, it can be seen that the color reproducibility is not impaired, and that particularly high discrimination is obtained. In addition, the present invention is an effective solution to the disappearance of high chroma red gradation. It turns out that it is a means.

[0107]

According to the digital color image forming method of the present invention, an image having excellent color reproducibility and gradation reproducibility can be obtained from information recorded on a magnetic recording material or the like by exposing a silver halide photographic material. Can be obtained.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/20

Claims (3)

(57) [Claims] 1. A method for forming a digital color image, comprising exposing a silver halide photographic material having a silver halide emulsion layer containing a yellow coupler, a magenta coupler and a cyan coupler on a reflective support, followed by developing. The chromaticity when the image density of the yellow color patch obtained by the color image forming method is 2.0 is metric when the metric hue angle is 86 degrees or more and 90 degrees or less in the CIE 1976 L ^* a ^* b ^* color space. The chroma is set to 85 or more, and the chromaticity when the image density of the magenta color patch becomes 2.0 is CIE 197.
6. A color image forming method, wherein a metric hue angle is 340 degrees or more and 355 degrees or less and a metric chroma is 70 or more in an L ^* a ^* b ^* color space. 2. A silver halide emulsion layer wherein at least one silver halide emulsion layer contains at least one of compounds having a Group VIII metal, a Group II metal, lead, rhenium, molybdenum, tungsten and chromium in the periodic table. 2. The color image forming method according to claim 1, wherein the exposure method is scanning exposure in which the exposure amount per pixel is 10 ^-4 seconds or less. 3. A silver halide emulsion containing a cyan coupler, wherein the exposure amount for a silver halide emulsion layer containing a yellow coupler and the exposure amount for a silver halide emulsion layer containing a magenta coupler are both exposure amounts that provide a high-density image. When the exposure amount for the layer satisfies the condition that the exposure amount gives a cyan image having a density of 0.5 or less, the exposure for the cyan coupler-containing silver halide emulsion layer is performed. 3. The color image forming method according to claim 1, wherein the exposure is performed at an exposure amount calculated so as to form an image having a higher contrast than an image formed on the emulsion layer.