JP2001264958A - Area gradation image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an area gradation image forming method with which a proof image is obtd. to prevent the occurrence of a fluctuation in colors, such as a three-color black image, in spit of the aging of a silver halide photosensitive material and a difference in the atmosphere at exposure. SOLUTION: This area gradation image forming method for subjecting the silver halide photosensitive material having silver halide emulsion layers on a base to development processing after scanning exposure at either of the exposure energy level of at least dot parts and the exposure energy level of cleaning parts is characterize in that the exposure energy level of clearing parts is set at the exposure energy of >=1/2 of the threshold at which development occurs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an area gradation image forming method capable of obtaining a proof for confirming the finish of a printed matter in advance, and more particularly to a method for forming a silver halide light-sensitive material over time and exposure. The present invention relates to an area gradation image forming method capable of obtaining a proof image excellent in stability without variation in color of a three-color black image due to a difference.

[0002]

2. Description of the Related Art Silver halide light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. I have.

Because of these characteristics, silver halide light-sensitive materials are widely used not only in the field of photography but also in the field of printing, in the field of so-called proofing for checking the state of a finished printed matter in the middle of printing. It is becoming.

In the field of proofing, an image edited on a computer is output to a printing film, and the developed film is appropriately replaced and separated and exposed to light for yellow (Y), magenta (M), and cyan (C). ), The image of the final printed matter is formed on a color photographic paper, thereby determining the layout of the final printed matter and the suitability of the colors.

In recent years, a method of outputting an image edited on a computer directly to a printing plate has gradually become widespread. In such a case, a color image is directly obtained from data on the computer without using a film. It was desired.

For this purpose, various methods such as a sublimation type / fusion heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method which can obtain a high quality image is expensive and requires high productivity. However, there is a disadvantage that the image quality is inferior in a system which is low in cost and has high productivity.

[0007] A system using a silver halide photosensitive material is capable of forming a high-quality image such as an accurate halftone dot image because of its excellent sharpness and the like. It is possible to realize high productivity because it is possible and an image can be written to a plurality of color image forming units at the same time.

In recent years, in the field of printing, so-called digitization has progressed and the demand for obtaining an image directly from data in a computer has been increasing. For the reasons described above, silver halide photosensitive materials have begun to be advantageously used in this field. I have.

[0009]

The problem to be solved by the present invention is to provide a proof image in which the color of a three-color black image or the like does not fluctuate due to the aging of the light-sensitive material and the difference in atmosphere during exposure. An object of the present invention is to provide a gradation image forming method.

[0010]

The above objects of the present invention have been attained by the following constitutions.

1. A method for forming an area gradation image, wherein a silver halide light-sensitive material having a silver halide emulsion layer on a support is subjected to scanning exposure and development processing at one of an exposure level of at least one halftone dot portion and an exposure level of a blank portion. 3. The area gradation image forming method according to claim 1, wherein the exposure level of the missing portion is set to an exposure amount equal to or more than 1/2 of a threshold value at which development occurs.

2. A method for forming an area gradation image, wherein a silver halide light-sensitive material having a silver halide emulsion layer on a support is subjected to scanning exposure and development processing at one of an exposure level of at least one halftone dot portion and an exposure level of a blank portion. 3. The area gradation image forming method according to claim 1, wherein the exposure level of the missing portion is an exposure amount in which the density difference between the missing portion and the non-image forming portion is 0.01 to 0.3.

3. In the characteristic curve of the silver halide emulsion layer, the exposure level dγ / d (log)
3. The method for forming an area gradation image according to the above 1 or 2, wherein H) is negative.

4. In the characteristic curve of the silver halide emulsion layer, there is a region where Δγ ≧ 0.5 between ΔlogH = 0.05, and the exposure level of the halftone dot portion is larger than the exposure amount of the region. 4. The area gradation image forming method according to any one of the above items 1 to 3, wherein

[0015] 5. The area gradation image forming method according to any one of the above items 1 to 4, wherein the sub-scanning pitch of the scanning exposure is 5 pixels or more.

That is, in a system for forming an area gradation image based on digital data, a halftone dot is divided into smaller units (here, these are expressed as pixels), and the pixels are exposed with an appropriate exposure amount. It is possible to reproduce a halftone dot as an aggregate by the above. As a simple example, if one halftone dot is composed of 100 pixels, halftone dots are formed by exposing 50 pixels so that halftone dots can be developed. You can do it. In the present specification, the pixel exposed in this example is referred to as a halftone portion, and the exposure amount at this time is referred to as an exposure level of the halftone portion. On the other hand, a pixel that is not exposed in this example is referred to as a missing portion.

The coloring density and the area of the coloring region change depending on the exposure amount, the exposure beam diameter, etc., and the dot percentage actually measured by using a densitometer differs from the number of exposed pixels. In practice, after setting the exposure amount and beam diameter in appropriate areas, the number of pixels to be exposed is appropriately changed, and the work of finely adjusting the exposure amount is repeated. The conditions will be adjusted so that the dot gain is reproduced.

While repeating the above-mentioned operations, the inventors of the present invention can adjust the dot gain of a single color such as yellow (Y), magenta (M), and cyan (C) in the same manner. When a pattern called a three-color black ink in which M, C and M are superimposed is produced, it is found that there is a phenomenon that the color tone is apt to fluctuate depending on the dot%. Because of this phenomenon, it has been found that the photographic material has aged, or that the color shift has increased when the atmosphere during exposure has changed, leading to the invention of the present invention. .

Hereinafter, the present invention will be described in more detail. One of the features of the present invention resides in that a specific amount of exposure is performed even on the above-mentioned blank portion in forming an area gradation image. The area gradation image is a so-called halftone dot image, and since it is composed of a colored portion and a non-colored portion, the missing portion can be omitted without exposure, but one of the features of the present invention is that In other words, the blank portion is exposed with an exposure amount equal to or more than の of a threshold value at which development occurs.

The threshold value at which development occurs can be easily determined by changing the exposure amount of the silver halide light-sensitive material and developing it after exposure to produce a so-called characteristic curve.
The greater the exposure, the greater the effect. The higher the exposure, the more inevitable coloring occurs. Therefore, it is necessary to appropriately adjust the exposure according to the purpose. The effect of the present invention can be obtained when the density difference between the non-image portion and the blank portion is in the range of 0.01 to 0.3, but a region having a density of 0.02 to 0.2 is more preferably used.

One of the features of the present invention resides in that the exposure level of the halftone dot portion exists in a region where dγ / d (logH) is negative on the characteristic curve. γ represents the slope of the tangent to the characteristic curve, and means dD / d (logH). The normal characteristic curve has a point of inflection in the middle density range to draw a gentle S-shaped curve, and dγ / d (logH) becomes negative on the higher density side. When the image forming exposure is performed in such an area, the color tone of the three black inks is likely to fluctuate due to the above-described dot gain change, and the effect of the present invention can be used more effectively.

Further, there is a phenomenon that a so-called two-step curve or a characteristic curve is bent by high-illuminance short-time exposure. In the case where such a phenomenon is shown, Δlog
When γ changes by 0.5 or more in a narrow region of H = 0.05, if the halftone dot portion is exposed with an exposure amount larger than this region, the color tone of three-color black or the like due to the above-mentioned dot gain change Is more likely to occur, and the effect of the present invention can be used more effectively.

One of the features of the present invention is that the exposure is performed by a scanning exposure apparatus having a sub-scanning pitch of 5 pixels or more, and the effect is more preferable when the sub-scanning pitch is large.

The silver halide emulsion used in the present invention is preferably a silver halide emulsion having 95 mol% or more of silver chloride, such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide. Those having an arbitrary halogen composition are used.

Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, particularly a silver halide emulsion having a portion containing silver bromide at a high concentration, is preferably used. Silver chloroiodide containing 0.05 to 0.5 mol% is also preferably used.

In the silver halide emulsion having a portion containing a high concentration of silver bromide, a portion containing a high concentration of silver bromide is
A so-called core-shell emulsion may be used, or a so-called epitaxy-bonded region in which a complete layer is not formed and only a region having a partially different composition may exist. 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 having 95% or more silver chloride used in the present invention preferably 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 that can be used for such purposes include irons, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and other Group 8-10 metals, cadmium, zinc, mercury and the like. 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 for the heavy metal ion to be contained in the silver halide emulsion, the heavy metal compound is subjected to various 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 any location.

In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound is dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The silver halide grains can also be prepared by forming silver halide fine grains containing these heavy metal compounds in advance and adding them.

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

The silver halide grains (hereinafter, also simply referred to as "grains") used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface.

Further, US Pat. No. 4,183,756,
No. 4,225,666, JP-A-55-26589,
Japanese Patent Publication No. 55-42737 and The Journal of
Photographic Science (J. Photog
r. Sci. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). 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, and 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.

The particle size can be measured by using the projected area of the particle or an approximate value of the 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 coefficient of variation 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 particle size distribution, and R represents the average particle size.) As a method for preparing a silver halide emulsion (hereinafter simply referred to as an emulsion), Various methods known in the art can be used.

The emulsion used in the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The emulsion may be grown at a 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-working silver halide emulsion 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. As sulfur sensitizers, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate,
Examples include cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer to be added is preferably changed depending on the type of silver halide emulsion to be applied, the size of the expected effect, and the like, but is preferably from 5 × 10 ^{-10 to} 5 × 10 ^-10 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 the 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 silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 1 per mol of silver halide.
It is preferably from 0 ^-4 mol to 1 × 10 ^-8 mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

As a chemical sensitization method for the negative working silver halide emulsion 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 generated during the preparation process of the silver halide light-sensitive material, to reduce fluctuations in performance during storage, and to prevent fog generated during development. And known antifoggants and stabilizers can be used.

Preferred examples of the compound which can be used for such a purpose include a compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, and more preferred specific examples are given below. Examples of such compounds include (IIa-1) to (IIa-) described on page 8 of the publication.
8), the compounds of (IIb-1) to (IIb-7), 1-
Compounds such as (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5-mercaptotetrazole, 1- (3-phenylacetamidophenyl) -5-mercaptotetrazole and the like can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitization step, completion of the chemical sensitization step, coating liquid preparation step and the like. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 1 mol per mol of silver halide is used.
It is preferably used in an amount of about ^0-4 mol. When added at the end of chemical sensitization, 1 × per mole of silver halide
An amount of about 10 ⁻⁶ mol to 1 × 10 ⁻² mol is preferable, and 1 ×
The amount is more preferably from 10 ⁻⁵ mol to 5 × 10 ⁻³ mol.

In the step of preparing the coating solution, when adding to the silver halide emulsion layer, 1 mol per mol of silver halide is used.
Preferably the amount of about × 10 ^-6 mol to 1 × 10 ^-1 mol, 1
More preferably, it is from × 10 ⁻⁵ mol to 1 × 10 ⁻² mol. Further, when added to a layer other than the silver halide emulsion layer, the amount in the coating film is, 1 m ² per 1 × 10 ^-9 mol to 1 × 10 ^{- 3}
Molar amounts are preferred.

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 silver halide light-sensitive material used in the present invention is colored with at least one diffusion-resistant compound 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.

The silver halide light-sensitive material used in the present invention comprises 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. The hydrophilic colloid 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 amount of the white pigment is preferably 0.1 g / m ^2.
５０50 g / m ² , more preferably 0.2 g / m ²
/ M ^{2 to 5} g / m ² .

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 arbitrary position. An aqueous colloid layer can be provided.

It is preferable to add a fluorescent whitening agent to the silver halide light-sensitive material used in the present invention since the 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.

The silver halide light-sensitive material used in the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any of known compounds can be used. As the blue sensitizing dye, JP-A-3-251840, page 28 BS-1 to 8 described in
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. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. Further, as a method for adding these dyes, they may be dissolved in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, and dimethylformamide and added as a solution, May be added as a solution, emulsion, or suspension in a water-miscible solvent having a density of more than 1.0 g / ml.

As a method for dispersing the sensitizing dye, other than a method of mechanically pulverizing and dispersing fine particles of 1 μm or less in an aqueous system using a high-speed stirring type disperser, see JP-A-58-105141.
No. 60-6496, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system under the conditions of pH 6 to 8 and 60 to 80 ° C. A method of dispersing in the presence of a surfactant suppressed to not more than × 10 ⁻⁴ N / cm, dissolving in an acid substantially free of water and having a pKa not exceeding 5 described in JP-A-50-80826, A method in which the solution is added and dispersed in an aqueous liquid, and the resulting dispersion is added to a silver halide emulsion can be used.

Water is preferable as the dispersion medium used for dispersion, but the solubility can be adjusted by adding a small amount of an organic solvent, or the stability of the dispersion can be enhanced by adding a hydrophilic colloid such as gelatin. .

Examples of the dispersing apparatus that can be used for preparing the dispersion include a high-speed stirring type dispersing apparatus shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, and an ultrasonic dispersing apparatus. And the like.

In using these dispersing apparatuses, a method of performing a pre-treatment such as dry pulverization in advance and then performing a wet dispersing method as described in JP-A-4-125632 may be employed.

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

As the coupler used in the silver halide light-sensitive material used in the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical ones are 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 50 to 50 nm.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of 0 to 600 nm, and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

As the magenta coupler used 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 the coloring dye. Specific examples of preferred compounds include Compound M- described on pages 8 to 11 of the same publication.
1 to M-19. Still other specific examples include compounds M-1 to M-61 and 235,913 described in EP 273,712, pp. 6-21.
Among the compounds 1-223 described on pages 36-92, there are other than the representative examples described above.

The magenta coupler 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. λL0.2 means that the maximum absorbance is 1. on the spectral absorbance curve of the magenta image.
A wavelength longer than the wavelength indicating 0 and having an absorbance of 0.2.

The magenta image forming layer of the silver halide light-sensitive material used in 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;
More preferably, it is within 1.5.

The preferred yellow coupler to be contained in the magenta image-forming layer of the present invention is a coupler represented by the general formula [Y-Ia] described in the right column on page 12 of JP-A-6-95283. Among the couplers represented by the general formula [Y-1] of the same publication, particularly preferred are those represented by the general formula [M-1]
When combined with the magenta coupler represented by the following formula, the pKa of the coupler represented by the combination [M-1] is 3
It is a coupler having a pKa value not lower than the above.

Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283, as well as JP-A-2-13954.
No. 2, 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, imidazole and azole 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, a 2-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are represented. You. Among them, preferred compounds are described in JP-A-6-9 / 1994.
General formula [C-I] [C-I] described on page 13 of No. 5283
I].

The azole cyan couplers preferably used in the present invention include the following general formulas [I] and [II]
Is a cyan coupler represented by

[0076]

Embedded image

In the general formula [I], when m1 is 0, R
₁ represents an electron-withdrawing group having a Hammett's substituent constant σ _P of +0.20 or more. When m1 is 1 or 2 or more, at least one of R ₁ and R ₂ has a Hammett's substituent constant σ _P of +0. .2
Represents 0 or more electron withdrawing groups.

The substituent having a substituent constant σ _P defined by Hammett of the cyan coupler represented by the general formula [I] of the present invention of +0.20 or more is specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl. , Phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, tetrazolyl and the like, and halogen atoms.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, and halogen-substituted arylsulfonyl; sulfinyl groups include alkylsulfinyl and arylsulfinyl; and sulfonyloxy groups include alkylsulfonyloxy and arylsulfonyloxy. Sulfamoyl groups include N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, and the like; phosphoryl groups include alkoxyphosphoryl, aryloxyphosphoryl, alkyl Phosphoryl, arylphosphoryl and the like; carbamoyl groups include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-
N-arylcarbamoyl and the like; acyl groups as alkylcarbonyl, arylcarbonyl and the like; acyloxy groups as alkylcarbonyloxy and the like; oxycarbonyl groups as alkoxycarbonyl and aryloxycarbonyl and the like; halogen-substituted alkoxy groups as α -Halogen-substituted alkoxy and the like; halogen-substituted aryloxy groups include tetrafluoroaryloxy and pentafluoroaryloxy; pyrrolyl groups include 1-pyrrolyl and the like; tetrazolyl groups include 1-tetrazolyl and the like.

In addition to the above substituents, trifluoromethyl, heptafluoroisopropyl, nonylfluoro-
A t-butyl group, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used.

In the general formula [I], among the substituents represented by R ₁ or R ₂ , the substituents other than the electron-withdrawing group include various types and are not particularly limited. , Alkyl, aryl, anilino, acylamino,
Sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryl Examples include oxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. As the aryl group, a phenyl group is preferable.

The acylamino group includes an alkylcarbonylamino group and an arylcarbonylamino group; the sulfonamide group includes an alkylsulfonylamino group and an arylsulfonylamino group; the alkylthio group and the alkyl component in the arylthio group; Groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 32 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched. The cycloalkenyl group has 3 to 12 carbon atoms,
Particularly, those having 5 to 7 are preferable.

As the ureido group, an alkylureido group,
An arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a 5- to 7-membered heterocyclic group is preferable, specifically a 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- A phenyltetrazol-5-oxy group or the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3 , 5-
Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group;
3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; spiro compound residue such as spiro [3.3] heptane-1-yl; bridged hydrocarbon compound residue bicyclo [2.2. 1] heptan-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

These groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

In the general formula [I], the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₁ includes:
For example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy,
Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle linked by N atom , Alkoxycarbonylamino, aryloxycarbonylamino, carboxyl and the like. Preferred among these are a hydrogen atom and an alkoxy, aryloxy, alkylthio, arylthio, nitrogen-containing heterocyclic group bonded by an N atom. is there.

In the general formula [I], examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₁ include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, a tetrazole ring and the like.

More specifically, the compound represented by the general formula [I] is represented by the following general formulas [I] -1 and [I] -2.

[0090]

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In the general formulas [I] -1 and [I] -2, at least one of R ₁ and R ¹¹ , R ₁ and R ¹²
At least one is an electron-withdrawing group having σ _P of 0.20 or more. Examples of these electron-withdrawing groups include the same groups as the electron-withdrawing groups of R ₁ and R ₂ in the general formula [I].

[0092] X ₁ has the same meaning as X ₁ in the general formula (I). In general formulas [I] -1 and [I] -2,
Among R ₁ , R ¹¹ and R ¹² , those which are not electron-withdrawing groups having σ _P of 0.20 or more represent a hydrogen atom or a substituent.

As the substituent, R in general formula [I]
₁ and R ₂ have the same meanings as the substituents other than the electron-withdrawing group.

In the general formula [II], R ₃ and R ₄ each represent an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more. And the same groups as the electron-withdrawing groups for R ₁ and R _{2 in} the above. However, the sum of the σ _P values of R ₃ and R ₄ is 0.65
That is all.

X ₂ has the same meaning as X ₁ in formula [I]. As the nitrogen-containing 5-membered heterocyclic ring formed by Z ₂ ,
Examples include a pyrazole ring, an imidazole ring, and a tetrazole ring. These 5-membered nitrogen-containing heterocycles may have a substituent.

More specifically, the compound represented by the general formula [II] is represented by the following general formula [II] -1 [II] -2.

[0097]

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In the general formulas [II] -1 and [II] -2,
R ₃ , R ₄ and X ₂ have the same meanings as in general formula [II]. R ²¹ represents a hydrogen atom or a substituent.

The substituent represented by R ²¹ is represented by the general formula [I]
And the same groups as the substituents other than the electron-withdrawing group described for R ₁ and R ₂ .

The following are specific examples of the cyan coupler preferably used in the present invention.

[0101]

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[0102]

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[0103]

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[0104]

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The above 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.

Specific examples of the yellow coupler include compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by Y-I-1 to Y-I-55, or compounds described in JP-A-3-241345. Compounds described on pages 11 to 14 of 209466 and compounds represented by Y-1 to Y-30 can also be preferably used. Further, JP-A-6-95283 2
Couplers represented by the general formula [Y-I] described on page 1 can also be mentioned.

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

The λL0.2 of the spectral absorption of a yellow image is described in JP-A-6-95283, page 21, right column, lines 1 to 24.
This is a value defined by the content described in the row, 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 from 1 × 10 ^-3 to 1 / mol per mol of silver halide.
Mole, preferably in the range of 1 × 10 ^-2 to 8 × 10 ^-1 mole.

In order to adjust the spectral absorption characteristics of the magenta, cyan and yellow images, it is preferable to add a compound having a color tone adjusting effect. As the compound for this, 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 compound represented by the general formula [HBS- -II].

In the light-sensitive material of the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition, if necessary, an intermediate layer,
A filter layer, a protective layer and the like can be provided.

The respective 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 the general formulas I and II described on page 3 of JP-A-2-66541, phenol compounds represented by the general formula IIIB described in JP-A-3-174150, and
Amine compounds represented by the general formula A described in JP-A-90445; compounds represented by the general formulas XII and XII described in JP-A-62-182741;
Metal complexes represented by I, XIV and XV are particularly preferred for magenta dyes. Also, a compound represented by formula I 'described in JP-A-1-19649 and JP-A-5-11417.
The compound represented by the general formula II described above is particularly preferable 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 used in the present invention, the water-insoluble emulsion usually has a boiling point of 150 ° C. or higher. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the boiling point organic solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalic esters such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate; phosphates 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.

As a preferred compound as a surfactant used for dispersing a photographic additive used in the light-sensitive material of the present invention and adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms in one molecule is preferable. And sulfonic acid groups or salts thereof. Specifically, JP-A-64-26
No. 854, A-1 to A-11.

A surfactant in which an alkyl group is substituted by a fluorine atom is also 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 used in 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 to prevent a silver halide emulsion layer. 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;
Compounds II-1 to II-14 described on page 17 and compound 1 described on page 17 are exemplified.

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, and particularly preferable compounds are those represented by formula II described in JP-A-1-250944.
A compound represented by the formula (I-3); a compound represented by the formula III described in JP-A-64-66646;
No. 240, UV-1L to UV-27L;
No. 1633, a compound represented by the general formula I
Compounds represented by general formulas (I) and (II) described in JP-A-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 specific examples of oil-soluble dyes include compounds 1-27 described on pages 8 to 9 of JP-A-2-842.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, proteins other than gelatin, A hydrophilic colloid such as a 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, in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability, a method disclosed in Japanese Unexamined Patent Application Publication No.
It is preferable to add a preservative and an antifungal agent as described in JP-A-157646.

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 light-sensitive material or the processed sample.

As the support used for 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 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 mass of 50 to 300 g / m ² and having a smooth surface 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.

As the support used in the present invention, either a support having random irregularities or a smooth support can be preferably used.

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 was 13% by mass for improving sharpness.
The above is preferred, and more preferably 15% by mass.

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 sides 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.

The value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, more preferably 0.12 μm.
m or less is more preferable because the effect of good gloss is obtained.

The light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion, 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 photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter, referred to as LED) is more preferably used.

As a laser, a semiconductor laser (hereinafter, referred to as a semiconductor laser)
LD) is preferably used because it is compact and the life of the light source is long.

On the other hand, LDs are used for applications such as optical pickups for DVDs and music CDs, bar code scanners for POS systems, and for applications such as optical communication, and are inexpensive.
In addition, it has the advantage that a relatively high output can be obtained. Specific examples of LD include aluminum, gallium, indium, arsenic (650 nm), indium,
Gallium phosphorus (700 nm), gallium arsenic phosphorus (610 to 900 nm), gallium aluminum arsenic (760 to 850 nm), and the like can be given. Recently, lasers that emit blue light have been developed,
At present, it is advantageous to use an LD as a light source longer than 610 nm.

As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted into half-wavelength light by an SHG element and emitted, and an appropriate light source is obtained since visible light is obtained. It is used as a light source in a green-blue region without any color. As an example of this type of light source, there is a light source (532 nm) in which a YAG laser is combined with an SHG element.

As a gas laser, a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), and a helium neon laser (about 54 nm) are used.
4 nm, 633 nm). In particular, a helium neon laser is preferably used as a light source for G light.

As the LED, an LED having the same composition as that of the LD is known, but various LEDs from blue to infrared have been put to practical use.

As the exposure light source used in the present invention, each laser may be used alone, or a combination thereof may be used as a multi-beam. In the case of an LD, for example, by arranging ten LDs, a beam composed of ten light beams can be obtained.

On the other hand, in the case of a helium neon laser, the light emitted from the laser is split into, for example, ten light beams by a beam separator.

In the case of an LD, the intensity of the exposure light source used in the present invention may be directly modulated to change the current flowing through each LD, or may be changed by an AOM (acousto-optical element). The intensity may be changed using a simple element. In the case of a gas laser, a device such as an AOM or an EOM (electro-optical element) is generally used.

The area gradation image according to the present invention does not express the shading on the image by the shading of the color of each pixel, but expresses the area of a portion colored to a specific density. It may be considered synonymous with a halftone dot.

In the case of normal area gradation exposure, the purpose can be achieved by developing Y, M, and C colors. More preferably, it is preferable to selectively use two or more exposure values so that black is formed at a density higher than the color density of a single color. In order to identify that a single color such as M or C has further developed into black, it is preferable to perform exposure by appropriately using three or more exposure amounts. In printing, a plate of a special color may be used, but in order to reproduce this, it is preferable to use four or more values of exposure for different exposures.

In the case of a laser light source, the beam diameter is 25
μm or less, more preferably 6 to 22 μm. When the thickness is less than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed is reduced. On the other hand, if it exceeds 25 μm, unevenness increases and the sharpness of the image deteriorates. By optimizing the beam diameter, writing of a high-definition image without unevenness can be performed at high speed.

In order to draw an image with such light, it is necessary for a light beam to scan over a silver halide photosensitive material, but the photosensitive material is wound around a cylindrical drum and rotated at a high speed while being perpendicular to the rotation direction. A cylindrical outer surface scanning method in which a light beam is moved in various directions may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical recess and exposed is preferably used. A plane scanning method may be adopted in which the polyhedral mirror is rotated at a high speed, and the silver halide photosensitive material conveyed thereby is exposed by moving a light beam at right angles to the conveying direction. In order to obtain a high-quality and large image, a cylindrical outer surface scanning method is more preferably used.

In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be accurately brought into close contact with a cylindrical drum. In order for this to be performed properly, it is necessary to convey accurately aligned.

The silver halide light-sensitive material used in the present invention is preferably used when the surface on the side to be exposed is wrapped outwardly so that the positioning can be performed more accurately. From the same viewpoint, the support used for the silver halide light-sensitive material used in the present invention has appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.

The diameter of the drum can be arbitrarily set in accordance with the size of the silver halide light-sensitive material to be exposed.
The number of rotations of the drum can be set arbitrarily, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like.
From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed, but specifically, 200 to 3000 per minute.
Rotation is preferably used.

The silver halide light-sensitive material can be fixed to the drum by mechanical means or by providing a large number of fine holes which can be sucked on the drum surface in accordance with the size of the light-sensitive material. The photosensitive material can be sucked and brought into close contact. It is important to bring the photosensitive material as close as possible to the drum in order to prevent troubles such as image unevenness.

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-
(Β- (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 color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0, more preferably pH 9.8. ~ 12.
Used in the range of 0.

The processing temperature for color development used in the present invention is preferably 35 ° C. to 70 ° C. 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 ° C 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, 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 used in 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 photosensitive material of the present invention may be a roller transport type in which the photosensitive material is transported between rollers arranged in a processing tank, and the photosensitive material may be fixed to a belt. An endless belt system may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed Alternatively, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can be used.

In the case of processing a large amount, it is usual to carry out a running process using an automatic developing machine. At this time, the smaller the replenishing amount of the replenisher, the more preferable. The method is to add a treating agent in the form of a tablet, and the method described in JP-A-94-16935 is most preferable.

[0159]

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

Example 1 A polyethylene-laminated paper having a mass per square meter of 115 g was obtained by laminating high-density polyethylene on one side and molten polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass on the other side. On the reflective support (Taber stiffness = 3.5, PY value = 2.7 μm), each layer having the layer constitution shown in the following Tables 1 and 2 is applied on the side of the polyethylene layer containing titanium oxide, and further on the back side Contains gelatin.
00g / m ^2, silica matting agent 0.65 g / m ² a multilayer silver halide light-sensitive material sample was coated No. 101 was produced.

The coupler was dissolved in a high boiling point solvent, ultrasonically dispersed and added as a dispersion. At this time, (SU-1) was used as a surfactant. In addition, (H-
1) and (H-2) were added. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The total amount of (F-1) is 0.04 g in each layer.
/ M ² .

[0162]

[Table 1]

[0163]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- Mixture of di-sec tetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a mass ratio of 1: 1: 2 SO-1: trioctylphosphine oxide SO-4: tricresyl phosphate PVP: polyvinyl Pyrrolidone

[0165]

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[0166]

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[0167]

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[0168]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0 and pH = 5.5. At the same time. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide 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 was performed 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 give an average particle size of 0.71 μm
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-101 was obtained.

The above compound (EMP-101) was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B101).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX Then in the preparation of EMP-101 , (A solution) and (B
Liquid) and the addition time of (Liquid C) and (Liquid D) were changed in the same manner as in EMP-101 except that the average particle diameter was 0.64 μm, the variation coefficient of the particle diameter distribution was 0.07, and the content of silver chloride was Monodisperse cubic emulsion EMP-102 having a ratio of 99.5 mol%
I got EMP-101 in the preparation of Em-B101
In the same manner except that EMP-102 was used instead of
B102 was obtained. A 1: 1 mixture of Em-B101 and 102 was used as a blue-sensitive emulsion.

(Preparation of Green-Sensitive Silver Halide Emulsion) EMP
In the preparation of -101, (Solution A) and (Solution B), (C
Monodisperse cubic emulsion (EMP-103) having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner except that the addition times of the (liquid) and (liquid D) were changed.
I got

The above-mentioned EMP-103 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain a green-sensitive silver halide emulsion (Em-G101).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX Then, in the preparation of EMP-103, (solution A) and (B
Liquid) and the addition times of (liquid C) and (liquid D), except that the average particle size was 0.50 μm, the coefficient of variation was 0.08, and the silver chloride content was 99.
A 5% monodisperse cubic emulsion EMP-104 was obtained. Em-
EMP instead of EMP-103 in the preparation of G101
Em-G102 was obtained in the same manner except that -104 was used. A 1: 1 mixture of Em-G101 and 102 was used as a green-sensitive emulsion.

(Preparation of Red-Sensitive Silver Halide Emulsion)
MP-103 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to obtain a red-sensitive silver halide emulsion (Em-
R101) was obtained.

Sodium thiosulfate 1.8 mg / mole AgX Chloroauric acid 2.0 mg / mole AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mole AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mole AgX Stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX Sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX STAB-1: 1-phenyl -5-mercaptotetrazole STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole

[0178]

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Next, in the preparation of EMP-103, (A
Solution E), the average particle diameter was 0.38 μm, the variation coefficient was 0.08, and the A monodispersed cubic emulsion EMP-105 having a silver content of 99.5% was obtained. Em-R101 was prepared in the same manner as in the preparation of Em-R101 except that EMP-105 was used instead of EMP-103.
102 was prepared. 1: 1 of Em-R101 and R102
Was used as a red-sensitive emulsion.

An LED is used as a light source for B in the main scanning direction.
By arranging the individual units, the timing of the exposure was adjusted little by little so that the same location could be exposed by ten LEDs. Also, an exposure head was prepared in which ten LEDs were arranged in the sub-scanning direction, and exposure for ten adjacent pixels could be performed at one time.

Also, a multi-AOM was combined with a G He-Ne laser as a light source so that the intensity could be changed independently as 10 beams, and the 10 beams were assembled so as to be arranged in the sub-scanning direction. As the R light source, ten LDs were arranged so that the beams were arranged in the sub-scanning direction, and were assembled so that the intensity was independently modulated.

The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 100 μm.

In the exposure section, air whose temperature and humidity were adjusted in advance was circulated so that the atmosphere (temperature and humidity) at the time of exposure could be constantly adjusted, and the conditions were adjusted to 25 ° C. and 30% RH.

The light intensity was changed by the above-described exposure apparatus to
A patch having a uniform exposure of 0 × 10 mm was prepared and processed under the following developing conditions.
The exposure amounts of 99, 1.49, and 1.53, the exposure amount of the development threshold, and the position of the inflection point of the characteristic curve were obtained. The density was measured using a 508 densitometer manufactured by X-Rite, and the spectral characteristics were Status T.

Processing step Processing temperature Time Replenishment amount Color development 35.0 ± 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 60-80 30 ° C. 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'-di The is added to make 1 liter amino stilbene sulfonate derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g water tank solution pH = 1
Adjust to 0.0 and replenisher to pH = 10.6.

Bleach-fixer tank solution 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 0.0g ammonium sulfite (40% aqueous solution) 27.5ml 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.

The positions of the inflection points on the characteristic curves were 0.83, 1.32, and 1.26 for each of Y, M, and C.

Next, as an exposure image, a halftone% of 50 is used in a pattern called a three-color black in which halftone dots of Y, M, and C are combined.
%, The missing part, and a portrait image were prepared.

The silver halide photosensitive material No. 101 is processed under the following exposure / development conditions A to E (the composition of the developing solution not particularly specified is the same as the above-described processing conditions), and the color difference of the three-color black pattern is measured using a spectral colorimeter CM manufactured by Minolta. −2022
Was measured using a xenon pulse light source with geometric conditions d-0 of illumination and light reception, and the value of L ^* a ^* b ^* with the light D50 of the 2 ° visual field auxiliary standard was determined, and the color difference was calculated.

The results are shown in Table 3 below. (Exposure / development condition A) (Exposure / development condition B) Temperature / humidity of exposed part 25 ° C. 30% RH 35 ° C. 30% RH Age of photosensitive material −55 ° C. 40% RH 1 week Development temperature 35 ° C. 36 ° C. Development time 45 seconds 50 sec. Halftone dot exposure level Exposure level 1 Exposure level 1 Blank exposure level Exposure level 2 Exposure level 3 Exposure / development conditions C to E show only exposure level of the dropout area in exposure / development condition B. An image was formed in the same manner as in the case of No. 6.

Exposure level 1: Exposure amount at which the Y, M, and C concentrations become 0.99, 1.49, and 1.53, respectively, at the exposure temperature and humidity, development temperature, and development time described in exposure / development condition A. Level 2: Exposure temperature and humidity described in exposure / development conditions A, exposure amount of 30% of development threshold at development temperature and development time Exposure level 3: Exposure temperature / humidity and development temperature described in exposure / development conditions B Exposure amount of 30% of development threshold in development time Exposure level 4: 45% of development threshold at exposure level 3
Exposure level Exposure level 5: 60% of development threshold at exposure level 3
Exposure level Exposure level 6: 90% of development threshold at exposure level 3
Exposure

[0193]

[Table 3]

As shown in Table 3, exposure and reference
The color change observed under the condition B in which the aging of the photosensitive material, the exposure atmosphere, and the processing conditions were varied with respect to the development condition A was hardly changed under the condition C, but was improved under the conditions D and E. I understand. It is a matter of course that the color changes due to the aging of the photosensitive material and changes in the development conditions, but it was an unexpected fact that this color change can be improved by changing the exposure level of the missing portion. It is preferable that the exposure amount is large, but it is understood that the effect of the present invention can be obtained if the exposure amount is 1/2 or more of the threshold value at which development occurs.

Example 2 In the evaluation of Example 1, the evaluation shown in the following Table 4 was carried out in the same manner as above except that the exposure amount of the blank portion was appropriately set to be equal to or higher than the development threshold value.

[0196]

[Table 4]

In the exposure and development conditions 2A to 2E, the exposure level in the blank portion was changed in the exposure and development condition B, and the density difference from the non-image portion was changed to about 0.3. It can be seen that the change in the color difference of the color ink portion is suppressed. It is thought that the coloring of the missing portion is caused by the coloring, but the coloring of the missing portion is more effective when the coloring is 0.2 or less.

Example 3 In the preparation of Sample 101 of Example 1, the coating amount of the silver halide emulsion and coupler in each layer was increased 1.5 times, and the mixing ratio of the emulsion was changed from 1: 1 to 7:13 for each layer. A sample 301 was prepared in the same manner as above except that the process was performed. The same evaluation as that of the sample 101 in Example 1 was performed except that the sample 301 was used. The positions of the inflection points of the characteristic curve of the sample 301 were 1.03, 1.63, and 1.58 for each of Y, M, and C.

The results of the evaluation are shown in Table 5 below.

[0200]

[Table 5]

The exposure level of the halftone dot portion was such that the Y, M, and C densities were 0.99, 1.49, and 1.53, respectively. The curve dγ / d (logH) exists in the negative region, and in the case of the sample 301, these points are represented by the d in the characteristic curve.
This means that γ / d (logH) exists in the positive region.

As shown in Table 5, although the variation in color is small by the area gradation image forming method of the present invention, the exposure level of the halftone dot portion is dγ / d of the characteristic curve.
It can be seen that the effect is greater in the sample 101 in which (logH) exists in the negative region.

Example 4 EMP-40 was prepared in the same manner as in Example 1 except that the amount of potassium hexachloroiridate (IV) used in preparing the silver halide emulsions EMP-101 to 105 was reduced to 1/2.
1-405 were prepared. Next, Em-B101, 102,
In the preparation of Em-G101, 102 and Em-R101, 102, silver halide emulsions EMP-101 to 105 were changed to EMP-401 to 405, and the same procedure was performed except that chloroauric acid was reduced to 1/2. Em-B40
1, 402, Em-G401, 402, Em-R40
1,402 were prepared.

In the preparation of sample 101 of Example 1, E
m-B101, 102, Em-G101, 102, Em
R101 and 102 were replaced with Em-B401 and 40, respectively.
2, Em-G401, 402, Em-R401, 402
A sample 401 was prepared in the same manner except that the sample was changed. As a result of preparing the characteristic curve of the sample 401, the characteristic curve was bent at the concentrations of 0.65, 1.13, and 1.34 for Y, M, and C, respectively. It was confirmed that the condition that the change was 0.5 or more was satisfied.
Therefore, it can be seen that the exposure level of the halftone dot portion is an exposure amount larger than these points. In Sample 101, such a bending of the characteristic curve was not found.

The results of evaluating the sample 401 in the same manner as in Example 1 are shown in Table 6 below.

[0206]

[Table 6]

Under the exposure / development conditions B and C which do not satisfy the requirements of the present invention, the color variation of the sample 401 is larger than that of the sample 101. It was found that a larger improvement effect was obtained although it did not exceed, and that the color fluctuation was reduced to almost the same level.

Embodiment 5 The light source used in Embodiment 1 was designed so that exposure for 10 pixels could be performed by one scan.
Adjustment was performed again so that exposure for three pixels and six pixels could be performed in each scan, and the same evaluation as in Example 1 was performed. The results are shown in Table 7 below.

[0209]

[Table 7]

It can be seen that the smaller the number of pixels that can be exposed in one scan, the smaller the color variation under the exposure and development conditions B and C, and the smaller the effect of improvement under the exposure and development conditions D and E. . Increasing the number of pixels that can be exposed in one scan has a large effect and is advantageous in reducing the time required for forming an entire image, but has the disadvantage that the above-described color fluctuations increase. The present invention has a large effect in such an aspect and can be used more effectively.

[0211]

The method for forming an area gradation image according to the present invention comprises:
A proof image in which the color does not fluctuate, such as a three-color black image, is obtained even when the silver halide light-sensitive material changes over time or the atmosphere during exposure, and has an excellent effect.

Claims (5)

[Claims] 1. An area in which a silver halide light-sensitive material having a silver halide emulsion layer on a support is subjected to scanning exposure and post-development processing at one of an exposure level of at least one halftone dot portion and an exposure level of a blank portion. An area gradation image forming method, wherein the exposure level of a blank portion is set to an exposure amount equal to or more than 1/2 of a threshold value at which development occurs. 2. An area in which a silver halide light-sensitive material having a silver halide emulsion layer on a support is subjected to scanning exposure and post-development processing at one of an exposure level of at least one halftone dot portion and an exposure level of a blank portion. An area gradation image forming method, wherein the exposure level of a blank portion is an exposure amount in which a density difference between a blank portion and a non-image forming portion is 0.01 to 0.3. . 3. In the characteristic curve of the silver halide emulsion layer, the exposure level d.gamma./d (log)
3. The area gradation image forming method according to claim 1, wherein H) is negative. 4. In the characteristic curve of the silver halide emulsion layer, there is a region where Δγ ≧ 0.5 between ΔlogH = 0.05, and the exposure level of the halftone dot portion is equal to the exposure level of the region. The area gradation image forming method according to claim 1, wherein the amount is larger than the amount. 5. The area gradation image forming method according to claim 1, wherein a sub-scanning pitch of the scanning exposure is 5 pixels or more.