JP2000267235A - Silver halide photosensitive material and formation of area gradation image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reproducibility of a black image in a silver halide photosensitive material, to improve reproducibility of single-color and black images, to provide a silver halide photosensitive material for a color proof having improved reproducibility of single-color and ink images and excellent characteristics such as continuous treating property, and to provide a method for the formation of an area gradation image for a color proof. SOLUTION: In this silver halide photosensitive material to form an area gradation image from four pieces of image information of yellow, magenta, cyan and black colors, the color whose dot % of a black image or a black image composed of four color is 100% is in 2 to 15 metric chroma and -55 deg. to -90 deg. hue angle in the CIELAB color space.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material excellent in reproducibility of a black image and a method for forming an area gradation image. More specifically, the present invention relates to a method for forming a black image using a silver halide emulsion. The present invention relates to a color proof silver halide light-sensitive material excellent in image reproducibility and a method for forming an area gradation image for color proof.

[0002]

2. Description of the Related Art Silver halide light-sensitive materials (hereinafter simply referred to as
It is widely used today because of its high sensitivity, excellent color reproducibility, and suitability for continuous processing. Due to these characteristics, silver halide light-sensitive materials have become widely used not only in the field of photography but also in the field of printing, in the field of so-called color proofing, which checks the state of finished printed matter during printing. Is coming.

In the field of color proofing, an image edited on a computer is output to a printing film, and the developed film is appropriately exposed and separated and exposed to light for yellow (Y), magenta (M), and cyan (M). By forming each image of C) and forming an image of the final printed matter on a color photographic paper, it has been performed to judge whether the layout and the color of the final printed matter are appropriate.

[0004] In printing, a black plate is used to improve the color reproducibility and the tightness of an image. Therefore, it is a great problem for a color proof material to properly reproduce the effect of the black ink.

However, there is a large difference in spectral absorption between an image dye used in a silver halide light-sensitive material and a pigment used in printing, and the degree of color formation varies due to changes in various conditions relating to development processing. There was a problem that the color shift was large when it was performed, and it was difficult to reproduce neutral gray to black.

In an image forming method using a silver halide light-sensitive material, variations in performance during the production of the light-sensitive material,
Fluctuations due to variations in development processing conditions, variations in the exposure amount at the time of exposure (fluctuations in wavelength other than fluctuations in light intensity) are inevitable, but at this time, the color image forming unit has four colors. That is, any silver halide photosensitive material capable of independently controlling and developing four colors in total, such as three colors of yellow, magenta, and cyan and a complementary color of black or any one of the three colors. For example, it is possible to form an image of black or four-color black with a color closer to neutral gray.

Further, if a single color, a secondary color, and black are set to different color development levels by taking a plurality of light intensity levels at the time of exposure, a black or four-color black image is formed with a color closer to neutral gray. It is possible to do.

[0008] However, such a method may cause other disadvantages such as a more complicated structure of the photosensitive material, an increase in cost, and a possibility that streak-like unevenness easily occurs due to a change in the exposure amount. Not always the best solution.

Although it is clear from the definition that the origin represents an achromatic color of white to black in the a ^* b ^* plane of the CIELAB color space, white is more preferable in the a ^* b ^* plane. It was known that it was far from it.

For example, JP-A-53-19021 discloses that
The surface reflection characteristic of the surface to which the image forming layer is applied is JIS Z
Measured according to the method specified in 8722, JIS Z873
L = 90 when represented by the method defined by 0
As described above, it is disclosed that the photographic support characterized in that a = 0.5 to 1.5 and b = -3 to -5 improves visual whiteness.

Japanese Patent Application Laid-Open No. 55-93150 discloses that the color of the white background of a printed photographic paper is W ^* = 86 or more and U ^* = − 1 to 1 in the U ^* V ^* W ^* color system. , V ^* = − 3 to
It discloses that whiteness can be improved by a silver halide photographic printing paper containing at least one oil-soluble dye in at least one photographic layer so as to fall within the range of -1.

However, there is no description as to whether or not the same can be said in the case of black, and no mention is made of the peculiarity of the area gradation image.

Further, silver halide photosensitive materials which obtain a monochrome image by processing with a color developing solution are commercially available. In addition, these photosensitive materials have in common that couplers of Y, M, and C are used in many cases.

However, some of these light-sensitive materials are for forming black-and-white images, while others are light-sensitive materials having a specific color tone such as sepia. To form.

[0015]

However, the invention of the present application is
This is related to a black image, and as can be understood from printing, it is not intended to form an image by itself, but a monochrome image that bears a part of a color image. There is a great difference from the invention described in (1).

The invention of the present application deals with an area gradation image, whereas the photographic material described in the above-mentioned prior art deals with a continuous gradation image. In the portion, the color-forming portion and the non-color-forming portion coexist, and the apparent spectral absorption of the image dye becomes broad. For light-sensitive materials handling area gradation images, compounds with sharper absorption than image dyes for continuous gradation images are required to compensate for the degradation of color reproduction due to this, and vivid color reproduction and stable gray There is a need for a balance of reproduction.

On the other hand, in the light-sensitive material described in the above-mentioned conventional technique, vivid color reproduction is not required, and the main focus is on obtaining gray stably with respect to fluctuations in an observation light source and development processing conditions. .

Accordingly, an object of the present invention is to improve the reproduction of a black image on a silver halide light-sensitive material, and to improve the reproducibility of a monochrome image and a black image.

More specifically, a silver halide light-sensitive material for color proof, which has the drawbacks of the silver halide light-sensitive material, that is, it has improved reproducibility of a monochrome image and a black image and has excellent characteristics such as continuous processability. An object of the present invention is to provide a method of forming an area gradation image for color proof.

[0020]

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

1. Yellow, magenta, cyan, and black 4
In a silver halide photosensitive material that forms an area gradation image by two pieces of image information, the color of 100% of the halftone image of the black or four-color black image has a metric chroma of 2 to 15 and a hue angle of −55 ° in the CIELAB color space. A silver halide light-sensitive material, characterized by being at an angle of -90 °.

2. Yellow, magenta, cyan, and black 4
Silver halide light-sensitive material that forms an area gradation image by three pieces of image information, the silver halide light-sensitive material has three color image forming units of yellow, magenta, and cyan, A color with 100% halftone of the image has a metric chroma of 2 in the CIELAB color space.
15. A silver halide photosensitive material having a hue angle of -55 ° to -90 °.

3. In the silver halide light-sensitive material, the color of 100% of the halftone image of the black or four-color black image is CIEL.
3. The silver halide light-sensitive material as described in 1 or 2, wherein the metric chroma is 2 to 13 and the hue angle is −60 ° to −85 ° in an AB color space.

4. Yellow, magenta, cyan, and black 4
Silver halide light-sensitive material that forms an area gradation image by three pieces of image information, the silver halide light-sensitive material has three color image forming units of yellow, magenta, and cyan, Image dot% is 40, 5
CIELA of 6 points of 0, 60, 70, 80, 100%
A silver halide, wherein a GOF value (expressed by the following formula 2) by a straight line passing through the origin determined by the least square method in the a ^* and b ^* planes of the B color space is 1.6 or less. Photosensitive material.

[0025]

(Equation 2)

The regression equation is expressed by ^{b * = α × a *,} b i is the measured value, b _i c represents the value calculated by the regression equation.
The subscript i represents an integer of 1 to 6 corresponding to the dot% of 40 to 100.

5. In the silver halide photosensitive material,
40%, 50, 60, 7
A GOF value of six points, 0, 80, and 100%, based on a straight line passing through the origin determined by the least square method in the a ^* , b ^* plane of the CIELAB color space is 1.0 or less. 5. The silver halide photosensitive material as described in 4 above.

6. In the silver halide photosensitive material,
At least one color image forming unit among the three color image forming units of yellow, magenta, and cyan is 64
6. The silver halide photosensitive material as described in any one of the above items 1 to 5, which has sensitivity to light having a wavelength longer than 0 nm.

7. A silver halide photosensitive material having three color image forming units of yellow, magenta, and cyan,
In a method of forming an area gradation image to be developed after exposing with a laser or a light emitting diode based on four image information of yellow, magenta, cyan and black, halftone% of the image of black or 4-color black is 40, 50, 60, A method for forming an area gradation image, wherein six points of 70, 80, and 100% are in a range of 2 to 15 metric chromas and a hue angle of -55 to -90 in a CIELAB color space.

8. In the method of forming an area gradation image, halftone% of an image of black or 4-color black is 40, 50, 6
Six points, 0, 70, 80, and 100%, are CIELAB
Metric chromas 2 to 13 in color space, hue angle -6
8. The method for forming an area gradation image according to the item 7, wherein the angle is in a range of 0 ° to −85 °.

9. A silver halide photosensitive material having three color image forming units of yellow, magenta, and cyan,
In a method of forming an area gradation image to be developed after exposing with a laser or a light emitting diode based on four image information of yellow, magenta, cyan and black, halftone% of the image of black or 4-color black is 40, 50, 60, GO of 70 points of 70, 80, and 100% by straight lines passing through the origin determined by the least squares method in the a ^* , b ^* plane of the CIELAB color space.
An area gradation image forming method, wherein the F value is 1.6 or less.

10. In the method of forming an area gradation image, halftone% of an image of black or 4-color black is 40, 50, 6
CIELAB of 6 points which are 0, 70, 80 and 100%
10. The area gradation image forming method according to the above item 9, wherein a GOF value based on a straight line passing through the origin determined by the least-squares method in the a ^* and b ^* planes of the color space is 1.0 or less.

11. Forming an area gradation image by developing a silver halide photosensitive material having three color image forming units of yellow, magenta and cyan with a laser or a light emitting diode after exposing it with four image information of yellow, magenta, cyan and black In the method, the dot percentage of the black or four-color black image is 40, 50, 60, 70, 80, 100.
%, The GOF value of a straight line passing through the origin determined by the least square method in the a ^* and b ^* planes of the CIELAB color space is 1.6 or less, and the 6 points are CIELAB.
Metric chroma 2-15, hue angle -5 in color space
A method for forming an area gradation image, which is in a range of 5 ° to -90 °.

12. Forming an area gradation image by developing a silver halide photosensitive material having three color image forming units of yellow, magenta and cyan with a laser or a light emitting diode after exposing it with four image information of yellow, magenta, cyan and black The method wherein at least one of the three color image forming units has only one color development level and the% of black or four color black image is 40;
CI of 50 points which are 50, 60, 70, 80 and 100%
The GOF value of a straight line passing through the origin determined by the least-squares method in the a ^* and b ^* planes of the ELAB color space is 1.6 or less, and the six points are metric chroma 2 to 15 and the hue angle in the CIELAB color space. A method for forming an area gradation image, which is in the range of −55 ° to −90.

13. In the method of forming an area gradation image, at least one of the three color image forming units of yellow, magenta, and cyan is developed after exposure to light having a wavelength longer than 640 nm. 13. The method for forming an area gradation image according to any one of 9 to 12 described above.

Hereinafter, the present invention will be described in more detail.

As is well known, the area gradation image expresses the color density by the size (area) of a point having a constant density. In the present invention, the area occupied by the dots having the constant density in the halftone dots is represented by the term "dot%". In the state where the color is uniformly applied to the entire halftone dot, the dot% is 100%, and the color is not applied at all, that is, the white state is 0%.

One feature of the present invention is that in a black or four-color black image, the color at the point where the dot percentage is 100% is in the range of 2 to 15 as metric chroma and -55 ° to -90 ° as hue angle. There is to be. The measurement of the color is performed, for example, according to JIS Z8.
722-1982 "Measurement Method of Object Color", and tristimulus values X, Y, Z were determined, and then JIS Z8
729-1980, "Method of Displaying Object Colors Using L ^* a ^* b ^* Color System and L ^* u ^* v ^* Color System", to achieve L ^* , a ^* , and b ^* .

In the measurement of the object color, it is preferable to use a measurement condition close to a normal observation condition. As a typical example, a light condition under the condition c of the geometric conditions of illumination and light reception of JIS Z 8729-1980 is used. The condition (d-0) using a trap is preferable. To obtain tristimulus values, a color matching function of a 2 ° visual field may be used as a color matching function, and standard light C may be used as colorimetric light. Instead of the standard light C, a standard light D65, an auxiliary standard light D50, or the like can be used.

Originally, the point of a ^* = 0 and b ^* = 0 is an achromatic color, and in the case of black ink or four-color black in which black, Y, M and C are combined, a value close to this is obtained. Is no doubt a preferred embodiment. However, in practice, it has been extremely difficult to properly reproduce these achromatic colors due to changes in various image forming conditions. This is easily achieved in a system using a black plate using a pigment such as printing ink, but the spectral absorption is different,
In addition, in the field of silver halide light-sensitive materials aiming at reproducing more vivid colors, it has been unavoidable.

What was unexpected, however, was that in some cases the degree of coloring was somewhat acceptable when the specific hue conditions were satisfied, but in many cases it was acceptable. The range of -55 ° to -90 ° as the hue angle is a color with a blue to magenta tint. In this case, up to 15 metric chroma is allowed. More preferable colors are colors in a range of -60 ° to -85 ° as a hue angle and 2 to 13 as a metric chroma.

One feature of the present invention is that the halftone percentage of an image of black or four-color black ink is 40, 50, 60, 70, 80, 100.
%, The GOF value of a straight line passing through the origin determined by the least squares method in the a ^* and b ^* planes of the CIELAB color space is 1.6 or less. It is more preferable that the GOF value is 1.0 or less.

The regression equation is represented by b ^* = α × a ^*.
In the above, b _i represents an actually measured value, and b _i c represents a value calculated by a regression equation. The subscript i represents an integer of 1 to 6 corresponding to the dot% of 40 to 100. The GOF value is a quantity indicating the degree of approximation of regression. The smaller the GOF value, the closer the distribution of points is to a straight line.

As a material for a color proof, contrast and sharpness have often been considered separately, and it has been considered that it is preferable that both materials show high values.

However, when the contrast is increased, the exposure latitude is narrowed, and the action to increase the sharpness generally involves a decrease in sensitivity, and it is difficult to realize the action even if an unduly high value is set. When both contrast and sharpness were at the level that achieved their goals, the task of assigning them to various performances and improving the overall performance was very important, but the solution has not yet been obtained. Had not been. The above condition is one solution to this problem, and when this condition is satisfied, comprehensively high performance can be obtained.

The silver halide emulsion used in the present invention may be a surface latent image type silver halide emulsion which forms a latent image on the surface by image exposure, or an internal latent image having a grain surface which is not previously fogged. Using an image-type silver halide emulsion,
An internal latent image type halogenation that can directly obtain a positive image by performing fogging treatment (nucleation treatment) after image exposure and then performing surface development, or performing surface development while performing fogging processing after image exposure It may be a silver emulsion. The internal latent image type silver halide emulsion is an emulsion containing silver halide grains having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. Say.

One preferred form of the silver halide light-sensitive material of the present invention is a negative-working silver halide emulsion.
A silver halide emulsion comprising 0 mol% or more of silver chloride is preferably used.

As long as it satisfies the above conditions, it may have any halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide. Silver chlorobromide containing the above, silver halide emulsion having a portion containing a high concentration of silver bromide among them is preferably used,
Silver chloroiodide containing 0.05 to 0.5 mol% of silver iodide near the surface is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy region in which only a region having a partially different composition may exist may be formed.

It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or discontinuously.

The negative working silver halide emulsion preferably having 90% or more of silver chloride preferably used in the present invention advantageously contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and softening on the shadow side.

Heavy metal ions which can be used for such purposes include metals belonging to Groups 8 to 10 such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt; cadmium, zinc and mercury. Group 12 transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.
These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, its ligands are cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia And the like.

Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable. In order to allow the silver halide emulsion to contain heavy metal ions, the heavy metal compound may be added to any of the steps during physical ripening before formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. May be added at the location.

In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step. In addition, silver halide fine particles containing these heavy metal compounds are formed in advance,
It can also be prepared by adding this.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol to 1 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ mol.
Mol to 5.times.10.sup.- ⁵ mol is preferred.

One preferred form of the silver halide emulsion used in the present invention is an internal latent image type silver halide emulsion which has not been previously fogged. The internal latent image type silver halide grains have a large photosensitive nucleus. A silver halide grain having a portion inside the grain, wherein a latent image is mainly formed inside the grain. The composition of the silver halide grains includes any silver halide, for example, 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 to a range of g / m ² for a defined period of time from about 0.1 seconds to about 1 second on a light intensity scale, When developed at 20 ° C. for 4 minutes using the following surface developer A that develops only the surface image of the grains not containing a silver halide solvent, another part of the same emulsion sample is similarly exposed to light. Is an emulsion showing a maximum density which is not more than 1/5 of the maximum density obtained when developing at 20 ° C. for 4 minutes with the following internal developing solution B for developing the image inside. More preferably, the maximum density obtained with the surface developer A is not greater than 1/10 of the maximum density obtained with the internal developer B.

(Surface developer A) Methol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Add water 1000 cc (Internal developer B) Methol 2 0.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Add water 1000 cc Addition of water Latent image silver halide emulsions include those prepared by various methods. For example, a conversion type silver halide emulsion described in U.S. Pat. No. 2,592,250 or described in U.S. Pat. Nos. 3,206,316, 3,317,322 and 3,367,778. A silver halide emulsion having internally chemically sensitized silver halide grains, or an emulsion having silver halide grains containing polyvalent metal ions described in U.S. Pat. No. 3,271,157, or U.S. Pat. No. 3,761,276 discloses a silver halide emulsion containing a dopant which is obtained by weakly sensitizing the surface of silver halide grains containing a dopant.
Nos. 524, 50-38525 and 53-2408
And silver halide emulsions described in JP-A Nos. 52-156614 and 55-127549.

Such an internal latent image type silver halide emulsion which has not been fogged in advance gives a positive image without performing reversal processing by performing surface fogging processing. Alternatively, the treatment may be performed chemically using a fogging agent, a strong developing solution may be used, and heat treatment may be performed.

The whole-surface exposure is performed by immersing or moistening the image-exposed photosensitive material in a developing solution or another aqueous solution, and thereafter performing uniform exposure over the entire surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength range of the photographic photosensitive material,
Further, high illuminance light such as flash light can be applied for a short time, or weak light can be applied for a long time. Further, the time of the entire surface exposure can be varied over a wide range so as to finally obtain the best positive image, depending on the photographic light-sensitive material, development processing conditions, type of light source used and the like. In addition, it is most preferable that the exposure amount of the entire surface exposure be given in a certain fixed range in combination with the photosensitive material.

Normally, when an excessive amount of exposure is given, the minimum density increases or desensitization occurs, and the image quality tends to decrease.

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

The particles used in the present invention may have any shape. One preferred example is (10
It is a cube having the 0) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666
No., JP-A-55-26589, JP-B-55-4273.
No. 7 and The Journal of Photographic
Science (J. Photogr. Sci.) 21, 3
9 (1973) and the like, particles having an octahedral, tetradecahedral, dodecahedral, etc. shape can be produced and used. Further, particles having a twin plane may be used.

As the grains used in the present invention, grains having a single shape are preferably used, but it is particularly preferred to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably, in consideration of other photographic properties such as rapid processing property and sensitivity. It is in the range of 0.2 to 1.0 μm.

This particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient. That is, two or more monodisperse emulsions having a coefficient of 0.15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S represents the standard deviation of the grain size distribution, and R represents the average grain size.) Various apparatuses and methods known in the art can be used for preparing silver halide emulsions. A method can be used.

The emulsion used in the present invention may be obtained by any of the acidic method, the neutral method, and the ammonia method. The particles may be grown at one time,
The seed particles may be grown after they are made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The negative silver halide emulsion preferably having 90% or more of silver chloride preferably used in the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, and inorganic sulfur.

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like, but is preferably 5 × 10 ^{−10 to} 5 × 10 −5 per mol of silver halide. In the range of ^10-5 mol, preferably 5
The range is preferably from × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As a gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 ×
10 ^-8 mol.

As a chemical sensitization method for a negative silver halide emulsion preferably having 90% or more of silver chloride preferably used in the present invention, a reduction sensitization method may be used.

The purpose of the silver halide emulsion used in the present invention is to prevent fog during the preparation process of the silver halide light-sensitive material, to reduce performance fluctuation during storage, and to prevent fog during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in
General formula (II) described in the lower column on page 7 of No. 146036
And more preferred specific compounds are (IIa-1) to (IIa-8), (IIb-1) to (IIb-) described on page 8 of the publication.
7) or 1- (3-methoxyphenyl) -5-
Compounds such as mercaptotetrazole, 1- (4-ethoxyphenyl) -5-mercaptotetrazole, 1- (3-phenylacetamidophenyl) -5-mercaptotetrazole and the like can be given. In an emulsion having a high silver bromide content, a tetrazaindene compound is preferably used. These compounds, depending on their purpose,
It is added in the steps of preparing the silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the coating liquid preparation step.

When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 mol / mol of silver halide is used.
It is preferably used in an amount of about × 10 ^-4 mol. When added at the end of chemical sensitization, 1 mole per mole of silver halide is used.
Preferably the amount of about × 10 ^-6 mol to 1 × 10 ^-2 mol, 1
More preferably, it is from × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. In the step of preparing a coating solution, when added to the silver halide emulsion layer, 1 × 10 ⁻⁶ mol to 1 × 1 mol per mol of silver halide is used.
The amount is preferably about 0 ^-1 mol, and 1 × 10 ^-5 mol to 1 × 1
0 ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

One feature of the present invention is that a silver halide emulsion having sensitivity to light having a wavelength longer than 640 nm is used in at least one of the color image forming units. In a silver halide photosensitive material having sensitivity to such long-wave light, particularly in a photosensitive material having a white reflective support,
Difficulty keeping sharpness high
The color tone at the point where the dot percentage is 40 to 80% in the LAB color space is likely to fluctuate, which is important as a means for obtaining the effects of the present invention.

In the light-sensitive material of 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 of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-251840.
The dyes of AI-1 to 11 described on page 308 and dyes described in JP-A-6-3770 are preferably used.

The following compounds can be exemplified as the infrared absorbing dye.

[0082]

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In the general formula [AI-1], R ^{1 to} R ⁶ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; L represents a substituted or unsubstituted methine group; Represents a cation, and n is 0 or a positive integer, and relates to the number of cations required to neutralize the charge.

Z ¹ and Z ^{2 each} represent a substituted or unsubstituted fused ring;
Z ¹ , Z ² , R ^{1 to} R ⁶ and L have at least 3 or more acid groups.

The silver halide light-sensitive material of the present invention is characterized in that at least one hydrophilic layer colored with a diffusion-resistant compound is provided on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferable to have a hydrophilic colloid layer. As the coloring substance, a dye or another organic or inorganic coloring substance can be used.

For this purpose, finely dispersed solid dyes can be used. The following compounds can be preferably used as such solid disperse dyes.

[0087]

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In the general formula [AI-2], R ⁷ , R ⁸ ,
R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. L ^{1 to} L ⁵ represent a methine chain. n1 and n2 represent the integer of 0-2. X ¹ and X ² each represent an oxygen atom or a sulfur atom.

As the inorganic compound, colloidal silver, colloidal manganese and the like are preferred, and colloidal silver is particularly preferred. Since these colloidal metals decolorize in the processing solution, they are also effective for the silver halide photosensitive material used in the present invention. The amount of colloidal silver to be used varies depending silver shape and purpose, preferably the amount of 0.01 to 0.3 g / m ^2, more preferably used in an amount of 0.02~0.1g / m ² . If the coating amount is too large, there is a problem that a white background becomes yellowish. From the viewpoint of reproduction of whiteness, it is preferable to use a small amount of yellow and black colloidal silver, and it is preferable not to use it.

The above colloidal silver, for example, gray colloidal silver, is prepared by reducing silver nitrate in gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol or dextrin while maintaining alkalinity;
After that, neutralize and cool to gelatinize the gelatin,
It is obtained by removing a reducing agent and unnecessary salts by a noodle washing method. When the reduction is performed under alkaline conditions, if the reaction is performed in the presence of an azaindene compound or a mercapto compound, a colloidal silver dispersion of uniform particles can be obtained.

The silver halide light-sensitive material of the present invention has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. Preferably, the layer may contain a white pigment. For example, rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin, and the like can be used, but among them, titanium dioxide is preferable for various reasons. The white pigment is dispersed in an aqueous binder of a hydrophilic colloid such as gelatin, which allows the processing liquid to penetrate. The coating with the amount of the white pigment is preferably in the range of ^{0.1g / m 2 ~50g / m 2} , more preferably in the range of ^{0.2g / m 2 ~5g / m 2} .

The average primary particle size of the white pigment used in the present invention is preferably from 0.30 μm to 3.0 μm.
More preferably, it is 0.32 μm to 1.0 μm. Here, the average primary particle size refers to a particle group of a white pigment observed with an electron microscope, and the cubic root of the particle volume at which the product of the particle volume and the frequency is the maximum is defined as the average particle size here.

This white pigment may be used alone or as a mixture of a plurality of different white pigments. When a plurality of white pigments having different average particle sizes are used in combination, the average primary particle size of the mixed white pigment may be 0.30 μm or more, or the average of any white pigment before mixing. It is sufficient that the primary particle size is 0.30 μm or more.

In the hydrophilic colloid layer having a white pigment,
For example, from the viewpoint of improving sharpness, it is preferable to include a light absorbing substance having a function of preventing halation by a support or a white pigment such as colloidal silver or a water-soluble dye, a solid dispersion of the dye, and the like. In such an image forming method, a sample having a dot percentage of 40 to 80% is useful as a means for adjusting the linearity of a point indicated in the CIELAB color space.

Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, if necessary, an undercoat layer or a non-photosensitive hydrophilic layer such as an intermediate layer at an optional position. An aqueous colloid layer can be provided.

It is preferable to add a fluorescent whitening agent to the silver halide light-sensitive material of the present invention since whiteness can be further improved.
The fluorescent whitening agent is not particularly limited as long as it is a compound capable of absorbing ultraviolet light and emitting visible light fluorescence, but one preferred embodiment is a compound having at least one sulfonic acid group in the molecule. And another preferable embodiment is a solid particulate compound having a fluorescent whitening effect.

As a preferable compound among the compounds having a sulfonic acid group in the molecule, a diaminostilbene-based fluorescent brightener having four or more sulfonic acid groups in a molecule, the upper right column on page 5 of JP-A-4-1633 General formula II described in
The compound shown by these can be mentioned. Specific examples of such a fluorescent whitening agent include compounds 1 and 2 described in JP-A-4-1633, page 5, lower right column to page 7, upper left column.
3 can be mentioned. Such a fluorescent whitening agent may be added to any layer such as a silver halide emulsion layer and a non-photosensitive layer, but is more preferably added to a non-photosensitive layer.
The addition amount of the fluorescent brightening agent is preferably ^{0.01~2g / m 2, 0.02~1g / m} 2 is more preferable.

The solid fine particle compound having a fluorescent whitening effect is a compound having a fluorescent whitening effect which is substantially insoluble in water, and a compound which is substantially unnecessary in water and has a fluorescent whitening effect at room temperature. Any type of compound can be used. Here, “substantially insoluble in water” means that at 25 ° C.,
It indicates that the solubility in 100 g of pure water is 1.0 g or less.

As the compound having a substantially water-insoluble fluorescent whitening effect, a general water-insoluble fluorescent whitening agent can be used.

In order to prepare a silver halide emulsion having a sensitivity to light having a wavelength longer than 640 nm used in the present invention, it is necessary to absorb light having such a wavelength and to sensitize the silver halide emulsion. Any known compounds can be preferably used as long as they can be used. Among them, a compound represented by the following general formula (SP-I) is preferable.

[0101]

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In the general formula (SP-I), Z ₁₁ and Z ₁₂
Is a benzoxazole nucleus, a benzothiazole nucleus,
It represents an atomic group necessary for forming a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus or a quinoline nucleus.

R ₁₁ and R ₁₂ each represent an alkyl group, an alkenyl group or an aryl group.

[0104] X ^- represents an anion, m is 0 or 1,
n represents the integer of 0-2.

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom, an alkyl group or an aryl group. When n represents 2, R ₁₆ and R ₁₇ may be the same or different.

The heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ is preferably a benzothiazole nucleus, a benzoselenazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, and a quinoline nucleus. The heterocyclic group represented by Z ₁₁ or Z ₁₂ may have a substituent, and preferred substituents include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group and the like. it can.

A particularly preferred halogen atom is a chlorine atom, and the aryl group is preferably a phenyl group.

The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, i-propyl, butyl and the like. Of these, a methyl group is preferable.

The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and includes methoxy, ethoxy, propoxy and the like. Among them, a methoxy group is preferable.

The alkyl group represented by R ₁₁ and R ₁₂ is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and more preferably a group such as methyl, ethyl, propyl and i-propyl. These alkyl groups may be substituted, and preferred substituents include a sulfo group, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an alkylsulfonylamino group.

Specifically, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, carboxymethyl, 2-carboxyethyl, 2-ethoxycarbonylethyl, 2-hydroxyethyl, 2-methylsulfonylaminoethyl and the like It is a group of.

The alkyl group represented by R ₁₁ and R ₁₂ is preferably an alkyl group substituted by a sulfo group or a carboxyl group.

The sulfo group, the carboxyl group and the like may form a salt with an organic cation such as a pyridinium ion and a triethylammonium ion or an inorganic cation such as an ammonium ion, a sodium ion and a potassium ion.

[0114] X ^- include anions represented by the chloride, bromide, and iodide ion or p- toluenesulfonate ion and the like are preferable, halide ions are preferred.

When forming an inner salt, an anion may not be contained, and in this case, m represents 0.

The alkyl group represented by R _{13 to} R ₁₇ is preferably a methyl group or an ethyl group, and R ₁₄ and R ₁₆ may form a ring. When n is 2, R ₁₆ may further form a ring.

Specific examples of the dye represented by formula (SP-I) include the following compounds.

[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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As the sensitizing dye represented by the general formula (SP-I), known compounds known as supersensitizers can be used. Preferred supersensitizers are shown below.

[0126]

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[0127]

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The silver halide light-sensitive material of the present invention contains 64
A silver halide emulsion spectrally sensitized to a region having a wavelength shorter than 0 nm may be used.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compounds can be used. As the blue-sensitive sensitizing dye, JP-A-3-251840 28 BS-1 described on the page
To 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

As a method of adding the sensitizing dye, the sensitizing dye may be dissolved in water or a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like, added as a solution, or added as a solid dispersion. It may be added.

The silver halide emulsion used in the present invention may contain one kind or a combination of two or more kinds of sensitizing dyes.

The coupler used in the silver halide light-sensitive material of the present invention can form a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Although any compound can be used, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a wavelength range of 500 to 600.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength at nm and cyan dye-forming couplers having a spectral absorption maximum wavelength at a wavelength range of 600 to 750 nm.

As the magenta coupler for use in the light-sensitive material of the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of excellent spectral absorption characteristics of a coloring dye. Specific examples of preferred compounds include compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Still another specific example is disclosed in EP-A-0,273,712, 6-2.
Compounds M-1 to M-61 described on page 1 and compounds 1 to 223 described in JP-A No. 0,235,913, pages 36 to 92, other than the above-mentioned representative specific examples, may be mentioned. .

The above magenta couplers can be used in combination with other types of magenta couplers.
1 × 10 ⁻³ mol to 1 mol, preferably 1 × 1 per mol
It can be used in the range of 0 ^-2 mol to 8 × 10 ^-1 mol.

The λmax of the spectral absorption of the magenta image formed in the light-sensitive material of the present invention is preferably 530 to 560 nm, and the λL0.2 is 580 to 63.
Preferably it is 5 nm.

Here, λL0.2 and λmax of the spectral absorption of the magenta image formed by the silver halide light-sensitive material of the present invention are amounts measured by the following method.

(Measurement Method of λL0.2 and λmax) When a positive emulsion is used as the light-sensitive material, a silver halide color photographic light-sensitive material is irradiated with a red light having a minimum light quantity capable of obtaining a minimum density of a cyan image. After uniformly exposing with a minimum amount of blue light to obtain the minimum density of the yellow image, and then subjecting it to white light through an ND filter and developing it, the integrating sphere is attached to the spectrophotometer. Attached, zero-corrected with a standard white plate of magnesium oxide, 500-70
The maximum value of the absorbance when measuring the spectral absorption at 0 nm is 1.
A magenta image is produced by adjusting the density of the ND filter so that it becomes zero. When a negative emulsion is used for the light-sensitive material, the density of the ND filter is adjusted so that when the magenta image is formed by applying green light through an ND filter and developing to form a magenta image, the same maximum absorbance as the above positive is obtained. I do. λL0.2 refers to a wavelength at which the absorbance of the magenta image is longer than the wavelength at which the maximum absorbance is 1.0 and the absorbance is 0.2 at the spectral absorbance curve.

The magenta image forming layer of the silver halide light-sensitive material of the present invention preferably contains a yellow coupler in addition to a magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. Preferred yellow couplers to be contained in the magenta image-forming layer of the present invention are described in JP-A-6-9.
It is a coupler represented by General Description General Formula [Y-Ia] described in the right column of page 12 of JP-A-5283. Particularly preferred couplers among the couplers represented by the general formula [Y-1] in the publication are those combined with the magenta coupler represented by the general formula [M-1] when combined with the coupler represented by [M-1] Is a coupler having a pKa value not lower than 3 or lower than the pKa lower than 3 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 JP-A-2-139.
No. 542, pages 13 to 17 (Y)
-1) to (Y-58) can be preferably used, but are not limited thereto.

As the cyan coupler contained in the cyan image forming layer in the light-sensitive material of the present invention, known phenol, naphthol or imidazole couplers can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, an oxygen atom introduced as a leaving group 2
Representative examples include an equivalent naphthol coupler. Of these, preferred compounds include the general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.

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

As the yellow coupler contained in the yellow image forming layer in the light-sensitive material of the present invention, known acylacetanilide-based couplers and the like can be preferably used.

As specific examples of the above yellow coupler,
For example, compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by Y-I-1 to Y-I-55,
Alternatively, compounds described on pages 11 to 14 of JP-A-3-209466 and compounds represented by Y-1 to Y-30 can also be preferably used. Further, JP-A-6-95283
And the couplers represented by the general formula [Y-I] described on page 21 of Japanese Patent Application Laid-Open Publication No. HEI 10-125, and the like.

The spectral absorption λmax of the yellow image formed by the light-sensitive material of the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.

The spectral absorption λ L0.
2 is JP-A-6-95283, page 21, right column 1
It is a value defined by the contents described in lines 24 to 24 and represents the magnitude of unnecessary absorption on the long wave side in the spectral absorption characteristics of the yellow dye image.

The yellow coupler is usually used in the silver halide emulsion layer in an amount of usually 1 × 10 5 per mole of silver halide.
^-3 to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol.

In order to adjust the spectral absorption characteristics of the magenta image, the cyan image and the yellow image, it is preferable to add a compound having a color tone adjusting action. As the compound for this purpose, the compounds represented by the general formulas [HBS-I] and [HBS-II] described on page 22 of JP-A-6-95283 are preferable, and more preferably, the compounds described in JP-A-6-95283.
It is a compound represented by the general formula [HBS-II] described on page 2.

The yellow image forming unit, the magenta image forming unit and the cyan image forming unit in the light-sensitive material of the present invention are laminated and coated on a support, but the order from the support may be any order. One preferred embodiment is, for example, a cyan image forming unit, a magenta image forming unit, and a yellow image forming unit from the side close to the support. In addition, an intermediate layer, a filter layer, a protective layer, and the like can be provided as necessary.

The color image forming unit used in the present invention may be considered in a narrow sense to be a layer containing a silver halide emulsion and a coupler, but it means a layer in which a color image is formed. When, for example, a layer containing only a silver halide emulsion is sandwiched between layers containing a coupler from both sides, these three layers constitute one image forming unit.

The present invention is more effective in a silver halide photosensitive material having only three color image forming units and an image forming method using the same. In particular, at least one color image forming unit has only one color development level. In such a case, the effect of the present invention is most useful because it is difficult to achieve both monochromatic and secondary colors and neutral gray to black reproduction.

The use of a silver halide emulsion having sensitivity to light of a specific long wavelength makes it difficult to achieve such a single color, secondary color, and neutral gray to black reproduction at the same time. ,
It has been found that the effects of the present invention are more greatly exerted under such conditions.

The magenta, cyan, and yellow couplers can be used in combination with a fading inhibitor to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, The amine compounds represented by the general formula A described in JP-A-64-90445 and the metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-182741 are particularly preferable for magenta dyes. Also, Japanese Patent Laid-Open No. 1-1960
The compound represented by the general formula I 'described in JP-A-49-49 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

When the oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide light-sensitive material of the present invention, the boiling point is usually 150 ° C.
The above-mentioned water-insoluble high-boiling organic solvent is dissolved, if necessary, in combination with a low-boiling and / or water-soluble organic solvent, 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 simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalic acid esters such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. And phosphine oxides such as trioctylphosphine oxide are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Preferred compounds as a surfactant used for dispersing a photographic additive used in the light-sensitive material of the present invention and adjusting the surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms in one molecule. And sulfonic acid groups or salts thereof. Specifically, JP-A-64-26
No. 854, A-1 to A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

In the silver halide light-sensitive material of the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication. .

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-66646.
Compound represented by general formula III described in
UV-1L to UV-27 described in JP-187240A
L, 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.

It is preferable that the light-sensitive material of the present invention contains an oil-soluble dye or pigment because the whiteness is improved. Representative examples of oil-soluble dyes are described in JP-A-2-842, pages 8-9.
Compounds 1 to 27 described on the page.

In the silver halide light-sensitive material of the present invention, it is advantageous to use gelatin as a binder. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, and non-gelatin polymers may be used. A hydrophilic colloid such as a protein, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used in the light-sensitive material of the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white paper, For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. which may contain a pigment can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the support having a water-resistant resin coating layer on the surface of paper, a support having a smooth surface having a weight of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, to approximate the sensation of handling the printing paper, 130 g / m ² or less of the base paper is preferably used, it is preferably used further 70~120g / m ² base paper.

The support having a water-resistant resin coating layer on the surface of paper used in the silver halide light-sensitive material of the present invention has a Taber Stiffness of 0.1.
It is preferably from 8 to 4.0. The Taber stiffness was measured using a stiffness meter V-5 model 150B Taber V
-5 Stiffness tester (TABER
INSTRUMENT-A TELEDYNE CO
MPANY). It is to be noted that the support generally has different stiffness values in the vertical and horizontal directions, but it is sufficient that at least one of the supports falls within this range. If the Taber stiffness is smaller than 0.8, there is a practical problem such as a transport failure in the automatic processing machine during continuous processing.

As the support used in the present invention, either a support having random irregularities or a support having a smooth surface can be preferably used. If it is smooth,
The unevenness of the surface of the support is continuously measured, and the measured signal is frequency-analyzed by Fast Fourier Transform. The power spectrum for each spatial frequency obtained by integrating the power spectrum in the frequency range of 1 to 12.5 mm (square root ( (PY value) is 2.9μ
m or less. More preferably 1.8μ
m or less, more preferably 1.15 μm or less. The lower limit is zero.

The surface unevenness can be measured using a film thickness continuous measuring device (for example, manufactured by Anritsu Corporation). The frequency of the obtained measurement signal can be analyzed using a frequency analyzer (for example, VC-2403 manufactured by Hitachi Electronics Co., Ltd.).

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are 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 amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, and more preferably 15% by weight, for improving sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support used in the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less as a coefficient of variation described in the above publication, and 0.15 or less.
It is more preferred that:

The resin layer of the paper support having a water-resistant resin layer on both surfaces used in the present invention may be a single layer or a plurality of layers. It is preferable to form a plurality of layers and to contain a high concentration of a white pigment in contact with the emulsion layer, since sharpness is greatly improved and an image for proofing is formed.

It is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less, since the effect that the glossiness is good can be obtained.

The light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion, antistatic property, It may be applied via one or more undercoat layers for improving degree stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.

In coating a 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.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-([Beta]-(methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9 ) 4-Amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N
-(Γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature of color development according to the present invention is 35
C. to 70 C. are preferred. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high, and the processing is preferably performed at 37 to 60 ° C.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide light-sensitive material of 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.

The developing apparatus used for developing the silver halide light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers disposed in a processing tank, or a photo-sensitive belt. An endless belt method may be used in which the material is fixed and transported.However, a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported or the processing liquid is sprayed. A spray method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. This is to add the treating agent in the form, and the method described in JP-A-94-16935 is most preferable.

Preferred embodiments of the present invention are shown below, but the present invention is not limited to these.

(1) In a silver halide photosensitive material that forms an area gradation image based on four pieces of image information of yellow, magenta, cyan, and black, the color of 100% of the black or 4-color black image is CIELAB. A silver halide photosensitive material having a metric chroma of 2 to 15 and a hue angle of -55 to -90 in a color space.

(2) In a silver halide photosensitive material which forms an area gradation image based on four pieces of image information of yellow, magenta, cyan, and black, the silver halide photosensitive material has three color images of yellow, magenta, and cyan. It has a formation unit, and 100% of halftone image of black or 4-color black image
Is a metric chroma 2 in the CIELAB color space.
A silver halide photosensitive material having a hue angle of from -55 ° to -90 °.

(3) In the silver halide light-sensitive material, the color of 100% of the halftone image of the black or four-color black image is CIE.
In the LAB color space, the metric chroma is 2 to 13, and the hue angle is −60 ° to −85 ° (1).
The silver halide light-sensitive material according to (2).

(4) In a silver halide photosensitive material which forms an area gradation image based on four pieces of image information of yellow, magenta, cyan and black, the silver halide photosensitive material has three color images of yellow, magenta and cyan. Having a forming unit, and the dot percentage of an image of black or 4-color black is 40, 5
CIELA of 6 points of 0, 60, 70, 80, 100%
A silver halide photosensitive material characterized by having a GOF value of 1.6 or less as a straight line passing through the origin determined by the least squares method in the a ^* , b ^* plane of the B color space.

(5) In the silver halide light-sensitive material, the dot percentage of the black or four-color black image is 40, 50, 6
CIELAB of 6 points which are 0, 70, 80 and 100%
The silver halide light-sensitive material according to (4), wherein the GOF value based on a straight line passing through the origin determined by the least squares method in the a ^* and b ^* planes of the color space is 1.0 or less.

(6) In the silver halide photosensitive material, at least one of the three color image forming units of yellow, magenta and cyan has sensitivity to light having a wavelength longer than 640 nm. The silver halide light-sensitive material according to any one of (1) to (5), wherein

(7) The silver halide light-sensitive material as described in (6), wherein the silver halide light-sensitive material contains a compound represented by the general formula [AI-1].

(8) The silver halide photosensitive material as described in (6), wherein the silver halide photosensitive material contains colloidal silver.

(9) The silver halide photosensitive material contains a white pigment on the side closer to the support than the layer closest to the support in the silver halide emulsion layer, and the white pigment has a particle size of 0.3.
The silver halide light-sensitive material according to (6), which has a thickness of at least μm.

(10) Three of yellow, magenta and cyan
In a method for forming an area gradation image in which a silver halide photosensitive material having two color image forming units is exposed and developed with a laser or a light emitting diode using four image information of yellow, magenta, cyan and black, black or 4 40%, 50, 60, 70, 80, 100
A method for forming an area gradation image, wherein 6 points, which are%, are in the range of metric chroma 2 to 15 and hue angle of −55 ° to −90 ° in the CIELAB color space.

(11) In the area gradation image forming method, the dot percentage of an image of black or 4-color black is 40, 50, 6
Six points, 0, 70, 80, and 100%, are CIELAB
Metric chromas 2 to 13 in color space, hue angle -6
Characterized by being in the range of 0 ° to -85 ° (10)
2. The method for forming an area gradation image according to item 1.

(12) Three of yellow, magenta and cyan
In a method for forming an area gradation image in which a silver halide photosensitive material having two color image forming units is exposed and developed with a laser or a light emitting diode using four image information of yellow, magenta, cyan and black, black or 4 40%, 50, 60, 70, 80, 100
The GOF value of a line passing through the origin determined by the least-squares method in the a ^* , b ^* plane of the CIELAB color space is 1.6 or less for the six points which are% in the area gradation image. Forming method.

(13) In the method of forming an area gradation image, halftone% of an image of black or 4-color black is 40, 50, 6
CIELAB of 6 points which are 0, 70, 80 and 100%
The method for forming an area gradation image according to (12), wherein the GOF value based on a straight line passing through the origin determined by the least square method in the a ^* and b ^* planes of the color space is 1.0 or less. .

(14) Three of yellow, magenta and cyan
In a method for forming an area gradation image in which a silver halide photosensitive material having two color image forming units is exposed and developed with a laser or a light emitting diode using four image information of yellow, magenta, cyan and black, black or 4 40%, 50, 60, 70, 80, 100
%, The GOF value of a straight line passing through the origin determined by the least square method in the a ^* and b ^* planes of the CIELAB color space is 1.6 or less, and the 6 points are CIELAB.
Metric chroma 2-15, hue angle -5 in color space
A method for forming an area gradation image, which is in a range of 5 ° to -90 °.

(15) In the method of forming an area gradation image, the dot percentage of an image of black or four-color black is 40, 50, 6
CIELAB of 6 points which are 0, 70, 80 and 100%
The GOF value of a straight line passing through the origin determined by the least squares method in the a ^* , b ^* plane of the color space is 1.0 or less;
The method for forming an area gradation image according to (14), wherein the six points are within a range of metric chroma 2 to 13 and a hue angle of −60 ° to −85 ° in the CIELAB color space.

(16) Three of yellow, magenta and cyan
In the method of forming an area gradation image in which a silver halide photosensitive material having two color image forming units is exposed and developed by laser or light emitting diode with four image information of yellow, magenta, cyan and black, the three colors are used. At least one of the image forming units has only one coloration level, and the dot percentage of an image of black or 4-color black is 40,
CI of 50 points which are 50, 60, 70, 80 and 100%
The GOF value of a straight line passing through the origin determined by the least-squares method in the a ^* and b ^* planes of the ELAB color space is 1.6 or less, and the six points are metric chroma 2 to 15 and the hue angle in the CIELAB color space. A method for forming an area gradation image, which is in the range of -55 ° to -90 °.

(17) In the method of forming an area gradation image, the dot percentage of an image of black or four-color black is 40, 50, 6
CIELAB of 6 points which are 0, 70, 80 and 100%
The GOF value of a straight line passing through the origin determined by the least squares method in the a ^* , b ^* plane of the color space is 1.0 or less;
The area gradation image forming method according to (16), wherein the six points are within a range of metric chroma 2 to 13 and a hue angle of −60 ° to −85 ° in the CIELAB color space.

(18) In the method of forming an area gradation image, at least one of the three color image forming units of yellow, magenta and cyan is developed after exposure to light having a wavelength longer than 640 nm. The method for forming an area gradation image according to any one of (11) to (17), wherein:

[0198]

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

Example 1 << Preparation of Emulsion EM-P1 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5) at the same time by the control double jet method.
A 30 μm cubic silver chlorobromide core emulsion was obtained. At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

To the obtained core emulsion, an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added by a control double jet method. The shell was formed until the average particle size became 0.42 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

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

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

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

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

Emulsions EM-P1 and EM-P2 were coated on a transparent cellulose triacetate support so that the amount of silver was 2 g / m ² as silver. Then, development was performed at 20 ° C. for 4 minutes using the surface developer A, a part of another sample was similarly exposed, and then developed at 20 ° C. for 4 minutes with the internal developer B. The maximum density for surface development was about 1/12 of the maximum density for internal development. EM-P1, EM-P2
Were both internal latent image type silver halide emulsions.

<< Preparation of Green-Sensitive Silver Halide Emulsion >> Emulsion E
After sensitizing dye GS-1 was added to M-P1 for optimal color sensitization, T-1 (4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene) in an amount of 600 m
g was added to prepare a green-sensitive emulsion Em-G1.

<< Preparation of Red-Sensitive Silver Halide Emulsion >> Emulsion E
Sensitizing dyes SP-I-21 and SP-I-22 on MP-2
Was added to obtain a red-sensitive emulsion Em-R1 in the same manner as the green-sensitive emulsion Em-G1 except that the color sensitization was optimal.

<< Preparation of Infrared-Sensitive Silver Halide Emulsion >> Red was prepared in the same manner as the green-sensitive emulsion Em-G1 except that the sensitizing dye SP-I-7 was added to the emulsion EM-P2 to optimize the color. An external photosensitive emulsion Em-IFR1 was prepared.

[0209]

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<< Preparation of Multilayer Silver Halide Photosensitive Material Sample >>
A polyethylene-laminated paper reflection support (weight: 115 g / square meter) laminated with high-density polyethylene on one side and fused polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by weight on the other side. = 3.5, PY value = 2.7 μm)
Using each emulsion of m-G1, Em-R1, and Em-IFR1, each layer having a layer constitution shown in the following Table 1 was coated on the side of the polyethylene layer containing titanium oxide, and 6.00 g of gelatin was further formed on the back side. / M ² , a multilayer silver halide photosensitive material sample No. 6 coated with a silica matting agent 0.65 g / m ² . 101 was produced. Incidentally, H-1 and H-2 were added as hardeners. As a coating aid and a dispersing aid, a surfactant SU-
1, SU-2 and SU-3 were added and prepared.

SU-1: sodium sulfosuccinate di (2-ethylhexyl) ester SU-2: sulfosuccinate di (2,2,3,3,4,4,
5,5-octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: tetrakis (vinyl) Sulfonylmethyl) methane

[0212]

[Table 1]

[0213]

[Table 2]

[0214]

Embedded image

[0215]

Embedded image

SO-1: trioctylphosphine oxide SO-2: di (i-decyl) phthalate HQ-1: 2,5-di (t-butyl) hydroquinone HQ-2: 2,5-di ((1, 1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone, 2,5-di-sectetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetra Mixture of decyl hydroquinone in a weight ratio of 1: 1: 2 T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-3: N-benzyladenine Helium-neon laser (544 nm) as a light source, semiconductor laser (650 nm) ), Semiconductor laser (780
After exposing the sample 101 to a laser printer of a drum exposure type having the following formula (nm), the following development processing was performed to obtain a black net image. Image is halftone, 0%, 40%, 50%
15x15m of%, 60%, 70%, 80%, 100%
A patch having a size of m was arranged in a row.

<< Processing Step >> Processing Step Temperature Time Immersion (Developer) 37 ° C. for 12 seconds Fog exposure −12 seconds Development 37 ° C. 95 seconds Bleaching and fixing 35 ° C. 45 seconds Stabilization processing 25-35 ° C. 90 seconds Drying 50-85 ° C. 40 seconds <Composition of color developer> Benzyl alcohol 15.0 ml Ethylene glycol 8.0 ml Diethylene glycol 15.0 ml Potassium sulfite 2.5 g Potassium bromide 1.0 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5. 0 g pentasodium diethylenetriaminepentaacetic acid 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Optical brightener (4,4′-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water to make the total volume 1000 ml, p Adjusted to 10.15.

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

<Composition of Stabilizing Solution> o-phenylphenol 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid 4.0 g diethylenetriaminepentaacetic acid 2.0 g ammonium hydroxide (28% aqueous solution) 0.7 g fluorescent whitening Agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Water is added to make the total volume 1000 ml, and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

[0220] The stabilization treatment was of a countercurrent type having a three-tank configuration.

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

<Composition of Color Developer Replenisher> Benzyl alcohol 18.5 ml Ethylene glycol 10.0 ml Diethylene glycol 18.0 ml Potassium sulfite 2.5 g Potassium bromide 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate Salt 5.0g Diethylenetriaminepentaacetic acid pentasodium 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water is added to adjust the total volume to 1 liter, and the pH is adjusted to 10.35.

<Composition of bleach-fix replenisher> Same as the above-mentioned bleach-fix solution.

<Composition of stabilizer replenisher> Same as the above stabilizer.

The replenishment rate was 320 ml per m ^{2 of} the photosensitive material for the developing solution, the bleach-fixing solution and the stabilizing solution.

Next, in the preparation of Sample 101, Samples 102 to 116 were prepared by changing the amounts of the silver halide emulsion and coupler in each layer by ± 7%. ± 15% according to the standard,
A 20% sample was also made. This was subjected to the same exposure and processing as in Sample 101, and then a Minolta Spectrophotometer CM-
In 2022, the photometry is performed using a xenon pulse light source under the geometric condition d-0 of illumination and light reception, and L ^* a ^* with light C of 2 ° visual field standard ^.
The value of b ^* was determined. A mask was prepared so that only half of the sample was visible at 100%, and the sample was presented to 10 subjects under a fluorescent light source for color evaluation. Judgment was required. The results were tabulated as 1 if acceptable and 0 if not. The results are shown in Table 3 below.

[0227]

[Table 3]

As shown in Table 3, when present in the metric chroma and hue angle regions of the present invention, it was accepted as black by more than half of the subjects. However, when the metric chroma and hue angle of the present invention are out of the range, the sample No. Very little outside this area, such as 102 and 104, was not acceptable to the majority of subjects.

From the nature of the CIELAB color space, the larger the metric chroma, the more achromatic color is deviated from. Therefore, it is expected that a larger metric chroma is disadvantageous. fact,
Sample No. having a metric chroma of more than 15 Sample No. 110 was completely unacceptable and had a high value of 13.3. 109 shows that the allowable ratio is low in the sample of the present invention.

However, the sample No. 109 and No. 104
It is also a fact that the slight difference in the hue angle overturns the disadvantage from the point of the metric chroma as shown in the above, and it can be seen that the metric chroma and the hue angle are complicatedly related. The hue angle is more preferably from 60 ° to 85 °, and the hue angle 70 °
It can be seen that the tolerance around ° is higher.

Example 2 Next, the sample No. For 101, 103, 105, and 109, the same processing as in Example 1 was performed by changing the light amount of the semiconductor laser of 650 nm by ± 15%, and
L ^* a ^* b for 50%, 60%, 70% and 80% points
^* Asked. Next, a GOF value was determined according to the definition of the above equation by approximating with a straight line passing through the origin in the a * b * plane. Next, this image was presented to the subject with the halftone percentage of 100% combined with the white background, and asked to determine the superiority or reproducibility of the reproducibility of the ink. Totals were added. The results are summarized in Table 4 below.

[0232]

[Table 4]

When the amount of exposure was changed, the hue shift was different depending on the difference in the spread of light at each wavelength and the difference in the gradation of each emulsion. With respect to 101, shows the swollen curve in the negative direction of the exposure -15% somewhat a ^*, the reference and + 15% level showed a swollen curves in the direction of positive a ^*.

Even if the reproduction level of the black ink is acceptable, if the GOF value is large, the color tone of the black ink becomes unstable, or the reproduction of the black ink is inferior due to the impression of lack of tightness. Come. As shown in Table 4, in the case where the GOF value exceeded 1.6, Sample No. Many evaluations such as 101 and 103 are inferior even if they are permitted. It shows the same movement as the GOF value, except that the metric chroma is 2 to 15 and the hue angle is -55 ° to -90.
When the number of points outside the region of ° (abbreviated as region A) increases, the evaluation of poor reproduction also increases. It is also important to reduce the GOF value by using such means as changing the amount of exposure in order to properly reproduce black.

Sample No. Exposure of 105 + 15% and N
o. When comparing the samples with the reference exposure amounts of 101 and 103, GO
Sample No. which is rather large as F value. It can be seen that 105 received higher evaluation. Thus, net% is 4
It is also found that whether or not all the points of 0% to 100% exist in the area A is also an important point.

When such an evaluation is performed, the point of the evaluation moves depending on whether or not the highlight side is reproduced in a natural neutral state. If the highlight side deviates from a straight line on the a ^* b ^* plane of the CIELAB color space, The difference in the tint was pointed out, and the evaluation was low, and the effect of the tint at the point where the halftone percentage was 100% on the evaluation was relatively low.

Example 3 Sample No. 1 of Example 1 In the preparation of 103, 105,
Sample No. 1 was prepared in the same manner except that the titanium dioxide in the first layer was changed from having an average primary particle size of 0.25 μm to having an average primary particle size of 0.35 μm. 201 and 202 were prepared. This sample was exposed and developed in the same manner as in Example 2 and evaluated.
The results are shown in Table 5 below.

[0238]

[Table 5]

The average of titanium dioxide contained in the first layer is 1
It can be seen that the GOF value is reduced by setting the secondary particle size to 0.35 μm. As a result, it can be seen that the result of the determination has also shifted to a direction in which more excellent black reproduction is recognized. Thus, it is useful to adjust the condition of titanium dioxide in the sense of adjusting the color tone of the region of the intermediate halftone%.

Example 4 Next, a silver halide photosensitive material was prepared using a negative-working silver halide emulsion containing silver chloride at a high concentration.

(Preparation of Infrared-Sensitive Silver Halide Emulsion) 4
In 1 liter of a 2% aqueous gelatin solution kept at 0 ° C., the following (solution A) and (solution B) were pAg = 7.3 and pH = 3.0.
At the same time while controlling to the following (liquid C) and (D)
Solution) was added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in JP-A-59-454.
The pH was controlled using a sulfuric acid or sodium hydroxide aqueous solution.

(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 102.7 g of potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml After desalting using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to obtain an average particle size of 0.40 μm
m, a coefficient of variation of 0.08, and a monodispersed cubic emulsion EMP-401 having a silver chloride content of 99.5% were obtained.

The above-mentioned EMP-401 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain an infrared-sensitive silver halide emulsion (Em-IR401).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer T-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer T-4 3 × 10 ⁻⁴ mol / mol AgX stability Agent T-5 3 × 10 ^-4 mol / mol AgX sensitizing dye SP-I-6 0.5 × 10 ^-4 mol / mol AgX sensitizing dye SP-I-7 0.5 × 10 ^-4 mol / mol AgX supersensitizer SS-10 2.0 × 10 ⁻³ mol / mol AgX T-4: 1-phenyl-5-mercaptotetrazole T-5: 1- (4-ethoxyphenyl) -5-mercaptotetrazole ( Preparation of green-sensitive silver halide emulsion) The above-mentioned EMP-401
The following compounds were optimally subjected to chemical sensitization at 55 ° C. to obtain a green photosensitive silver halide emulsion (Em-G401).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer T-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer T-4 3 × 10 ⁻⁴ mol / mol AgX stability Agent T-5 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-14 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) EMP-401
The following compounds were optimally subjected to chemical sensitization at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R401).

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer T-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer T-4 3 × 10 ⁻⁴ mol / mol AgX stability Agent T-5 3 × 10 ^-4 mol / mol AgX Sensitizing dye SP-I-12 1 × 10 ^-4 mol / mol AgX Sensitizing dye SP-I-13 1 × 10 ^-4 mol / mol AgX Supersensitizing Sensitizer SS-10 2.0 × 10 ⁻³ mol / mol AgX Using the silver halide emulsion thus prepared, silver halide light-sensitive materials Nos. 41
0 was produced.

[0247]

[Table 6]

[0248]

[Table 7]

[0249]

Embedded image

Since a negative silver halide emulsion was used,
The development was changed as follows.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60 ８０80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β-hydroxyethyl) -4-aminoaniline sulfate 2.9 g 4.8 g N, N-diethylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank solution was pH = 1.
Adjust to 0.0 and replenisher to pH = 10.6.

Bleach-fixing solution tank replenisher and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 7.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP ( Polyvinylpyrrolidone) 1.0 g Aqueous ammonia (25% ammonium hydroxide aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia. adjust.

Although the pattern of the produced image is the same,
The half-tone% of the Y, M, and C single colors is adjusted so that the exposure amount of 100% matches the Y, M, and C densities of the samples 101 and 102 of Example 1, and the exposure amount of the black plate is adjusted accordingly. 411, 41
2 was produced.

[0256]

[Table 8]

The evaluation results were in accordance with the color tone, and no particular difference was observed. Samples 411 and 412 did not cause any particular problem, but some stripe-like unevenness in exposure was observed.

Next, the evaluation of the region where the ink percentage was 40% to 100% was performed using the above sample No. Table 9 shows the results obtained in the same manner as in Example 2 under the conditions of 411.

[0259]

[Table 9]

The sample No. The sample prepared under the same conditions as in Sample 411 also had a GOF value of Sample No. The exposure value was almost the same as that of the exposure amount of 101% -15%, and the judgment result was also almost the same.
Sample No. If the exposure is performed under the condition 412 when a single color is developed in 401 and under the condition 411 when the black color is developed, the color image forming unit has two or more color development levels. Can be obtained. In other words, it is possible to correct the color closer to an achromatic color, which is advantageous. However, in such a case, G is simply used like increasing or decreasing the exposure amount.
Although there is no means for adjusting the OF value, and this embodiment does not cause a major drawback, there is a fear of streak-like unevenness.

The present invention is particularly useful when the color image forming unit can have only one color development level.

Example 5 Sample No. 1 of Example 1 Using 101 to 116, an area gradation image was produced with the following exposure apparatus.

(Exposure Apparatus) Infrared light source: semiconductor laser (GaAlAs: 785n)
m) Red light source: Semiconductor laser (AlGaInAs: 650n)
m) Green light source: HeNe laser (544 nm) The photosensitive material is suction-contacted to the rotating drum and the number of rotations is 2,000.
The rotation was performed at a rate per minute, and the image was recorded. At that time, twelve semiconductor lasers were arranged, and the silver halide photosensitive material was simultaneously exposed to the silver halide photosensitive material as twelve laser beams via optical means. The HeNe laser was divided into twelve laser beams modulated using an acousto-optic device and exposed. In any of the silver halide light-sensitive materials of the present invention, images excellent in color reproducibility and black image reproducibility could be obtained.

[0264]

As demonstrated in the examples, the present invention was able to improve the reproducibility of a black image on a silver halide light-sensitive material, and was also able to improve the reproducibility of monochromatic and black images.

More specifically, the silver halide light-sensitive material for color proof and the method of forming an area gradation image for color proof according to the present invention have improved reproducibility of a monochromatic image and a black image, and have excellent processing properties such as continuous processing. Has an effect.

Claims (13)

[Claims] 1. A silver halide photosensitive material that forms an area gradation image based on four pieces of image information of yellow, magenta, cyan, and black, wherein a half% of the black or four-color black image is 1%.
A silver halide photosensitive material characterized in that 00% of the color has a metric chroma of 2 to 15 and a hue angle of -55 to -90 in a CIELAB color space. 2. A silver halide photosensitive material for forming an area gradation image based on four pieces of image information of yellow, magenta, cyan and black, wherein the silver halide photosensitive material forms three color images of yellow, magenta and cyan. The color of 100% of the halftone image of the black or 4-color black image has a metric chroma of 2 in the CIELAB color space.
15. A silver halide photosensitive material having a hue angle of -55 ° to -90 °. 3. In the silver halide light-sensitive material, the color of 100% of the halftone image of black or 4-color black is CIELA.
In the B color space, metric chromas 2 to 13, hue angle −
3. The silver halide light-sensitive material according to claim 1, wherein the angle is from 60 [deg.] To -85 [deg.]. 4. A silver halide light-sensitive material for forming an area gradation image based on four pieces of image information of yellow, magenta, cyan and black, wherein the silver halide light-sensitive material forms three color images of yellow, magenta and cyan. The unit has 40% or 5% of black or 4-color black image.
CIELA of 6 points of 0, 60, 70, 80, 100%
A silver halide, wherein a GOF value (represented by the following formula 1) based on a straight line passing through the origin determined by the least squares method in the a ^* , b ^* plane of the B color space is 1.6 or less. Photosensitive material. (Equation 1) The regression equation is represented by b ^* = α × a ^* , where b _i is the measured value and b _i c
Represents a value calculated by a regression equation. Subscript i is net%
It represents an integer of 1 to 6 corresponding to 40 to 100. 5. In the silver halide light-sensitive material, the dot percentage of an image of black or four-color black is 40, 50, 60, 7
A GOF value of six points, 0, 80, and 100%, based on a straight line passing through the origin determined by the least square method in the a ^* , b ^* plane of the CIELAB color space is 1.0 or less. The silver halide light-sensitive material according to claim 4. 6. In the silver halide photosensitive material, at least one of the three color image forming units of yellow, magenta and cyan is 640.
6. The silver halide light-sensitive material according to claim 1, which has sensitivity to light having a wavelength longer than nm. 7. An area in which a silver halide light-sensitive material having three color image forming units of yellow, magenta and cyan is exposed and developed with a laser or a light emitting diode by using four image information of yellow, magenta, cyan and black. In the method of forming a gradation image, six points where the dot% of the black or four-color black image is 40, 50, 60, 70, 80, and 100% are metric chroma 2 to 15, hue angle in the CIELAB color space. A method for forming an area gradation image, which is in the range of -55 ° to -90 °. 8. The method of forming an area gradation image,
40%, 50, 60, 7
Six points, 0, 80, and 100%, have metric chromas 2 to 13 and hue angles of -60 to-in the CIELAB color space.
The method for forming an area gradation image according to claim 7, wherein the angle is in a range of 85 °. 9. An area in which a silver halide photosensitive material having three color image forming units of yellow, magenta and cyan is exposed after exposure with a laser or a light emitting diode using four image information of yellow, magenta, cyan and black. In the method of forming a gradation image, in the a ^* and b ^* planes of the CIELAB color space, there are six points where the dot% of the black or four-color black image is 40, 50, 60, 70, 80, and 100%. GOF by a straight line passing through the origin obtained by the least squares method
A method for forming an area gradation image, wherein the value is 1.6 or less. 10. The method of forming an area gradation image, wherein halftone percentages of black or four-color black images are 40, 50, 6
CIELAB of 6 points which are 0, 70, 80 and 100%
10. The area gradation image forming method according to claim 9, wherein a GOF value based on a straight line passing through the origin determined by the least square method in the a ^* and b ^* planes of the color space is 1.0 or less. . 11. A silver halide photosensitive material having three color image forming units of yellow, magenta and cyan,
In a method of forming an area gradation image to be developed after exposing with a laser or a light emitting diode based on four image information of yellow, magenta, cyan and black, halftone% of the image of black or 4-color black is 40, 50, 60, GO of 70 points of 70, 80, and 100% by straight lines passing through the origin determined by the least squares method in the a ^* , b ^* plane of the CIELAB color space.
The F value is 1.6 or less, and the above six points have a metric chroma of 2 to 15 and a hue angle of −55 ° in the CIELAB color space.
A method for forming an area gradation image, which is in the range of -90 [deg.]. 12. A silver halide light-sensitive material having three color image forming units of yellow, magenta and cyan,
In a method for forming an area gradation image which is developed by exposing and developing with a laser or a light emitting diode using four image information of yellow, magenta, cyan and black, at least one of the three color image forming units has only one color development level. No, 40% or 5% of black or 4-color black image
CIE of 6 points which are 0, 60, 70, 80, 100%
The GOF value of a straight line passing through the origin determined by the least squares method in the a ^* and b ^* planes of the LAB color space is 1.6 or less, and the six points are metric chroma 2 to 15 and the hue angle in the CIELAB color space. A method for forming an area gradation image, which is in the range of −55 ° to −90. 13. The method of forming an area gradation image, wherein at least one of the three color image forming units of yellow, magenta, and cyan is developed after exposure to light having a wavelength longer than 640 nm. The method of forming an area gradation image according to claim 9, wherein: