JPH08146573A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide color photosensitive material not deteriorating the color tone of magenta even if a high-silver chloride emulsion is used when colorproof is generated from the dot image information obtained by color separation and dot image conversion with the silver halide color photosensitive material and to provide a color image forming method. CONSTITUTION: This silver halide photosensitive material having a photosensitive structural layer containing at least one layer of silver halide emulsion on a base contains a silver halide emulsion having the percentage content of 80mol.% or above for silver chloride on at least one silver halide emulsion-containing layer, a magenta coupler and a yellow coupler are contained in a green photosensitive emulsion layer, a green photosensitive emulsion is contained in a blue photosensitive emulsion layer containing the yellow coupler, or the green photosensitive emulsion layer containing the yellow coupler is provided in addition to the blue photosensitive emulsion layer containing the yellow coupler and the green photosensitive emulsion layer containing the magenta coupler. This silver halide color photosensitive material attains the ratio (DB/DG) of 0.3-0.6 of the blue color density against the green color density at the low density section (DG=0.5) and the high density section (1.5) at the time of green color separation exposure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material and a color image forming method using the same, and more particularly, to a color image for proofing (color proof) from a transmission type black and white halftone original which is color-separated from a color original. ) Is suitable for producing a silver halide color light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, in the process of color plate making / printing, the drawbacks of the overlay method and the surprint method used as a method for obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone conversion have been considered. As an improvement, a method of using a silver halide color light-sensitive material is disclosed in JP-A Nos. 62-280747 to 280750 and 62-280849. However, the silver halide emulsions used in these are silver chlorobromide emulsions having a high silver bromide content, and there is no description sufficient to put into practical use a high silver chloride emulsion having rapid development and environmental compatibility. Even with light-sensitive materials for color proofing,
Practical use of high silver chloride emulsions that can improve the working environment and environmental suitability is required.

Recently, the field of use has come to be used not only for checking the position of characters and pictures but also for checking the color tone, and the quality demanded by the market is increasing. Since the printing ink and the dye of the photographic light-sensitive material have different spectral absorptions, the photographic light-sensitive material for proofing is approximated to the color of the printing ink by using various techniques.
Particularly for magenta, a method of mixing a magenta coupler and a yellow coupler is described in JP-A-2-139542.

However, when a high silver chloride emulsion is used, even if a magenta coupler and a yellow coupler are mixed as in the case of a silver chlorobromide emulsion, the color tone difference between the high density portion and the low density portion is large, and the density and the dots are large. When the gain is adjusted, the hue is greatly deviated, or the density needs to be extremely increased to match the hue, which is a practical problem.

Therefore, it has been desired to use a high silver chloride emulsion that does not cause a failure in magenta hue.

[0006]

In contrast to the above problems, the object of the present invention is to provide halftone image information obtained by color separation and halftone image conversion using a silver halide color photographic light-sensitive material. To provide a silver halide color photographic light-sensitive material (hereinafter also referred to as "color light-sensitive material") and a color image forming method in which a magenta color tone is not deteriorated when a color proof is prepared from is there.

[0007]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having a photosensitive constituent layer containing at least one silver halide emulsion layer on a support and containing the silver halide emulsion. A blue-sensitive emulsion layer containing a yellow coupler, which contains at least one silver halide emulsion having a silver chloride content of 80 mol% or more, and contains a magenta coupler and a yellow coupler in the green-sensitive emulsion layer. By incorporating a green photosensitive emulsion or having a blue photosensitive emulsion layer containing a yellow coupler and a green photosensitive emulsion layer containing a yellow coupler in addition to a green photosensitive emulsion layer containing a magenta coupler, it is possible to obtain Ratio of blue light density to green light density (DB / DG)
0.3 to 0.3 in the low density part (DG = 0.5) and the high density part (1.5)
This is achieved by using a silver halide color photographic light-sensitive material having a value of 0.6.

The present invention will be described in more detail below.

The constitution of the silver halide photographic light-sensitive material which achieves the object of the present invention can be specifically realized by the following method.

A yellow coupler is mixed in the magenta coloring green photosensitive layer. The pKa of the coupler to be mixed is preferably 0.1 to 2.5 smaller than that of the magenta coupler. More preferably, it is 0.2-2. The addition amount depends on the combination of couplers, but is 0.02 by weight ratio to the magenta coupler.
0.6 is preferable.

The pKa of the coupler will be described below. Ka is the dissociation constant of the coupler. As the measurement conditions, the spectral absorption was measured with MCPD-110 (manufactured by Union Giken Co., Ltd.), and the pKa was obtained as follows. 80% ethyl alcohol was used as the measurement solvent.

[0012]

[Equation 1]

From the above equation, the pH of the solution in which the free coupler and coupler anion are present in equimolar (1: 1) represents the pKa of the coupler.

A green photosensitive emulsion is added to the yellow color developing blue photosensitive layer. Is the sensitivity the same as magenta coloring green sensitivity,
Somewhat low is preferable (magenta layer ratio 1 to 0.5). The amount to be added is preferably 0.02 to 0.5.

A yellow coloring green photosensitive layer is provided. The sensitivity is preferably the same as or slightly lower than that of the magenta color-forming green photosensitive layer. The layer structure may be adjacent to the magenta color forming photosensitive layer or may be provided with an intermediate layer. It is preferable to provide an intermediate layer between the other emulsion layers.

The methods (1) to (4) may be used alone or in combination with other methods.

DB / DG is a Ratten No. 61 (manufactured by EK) was wedge-exposed to green separation light, and the developed sample was measured with a densitometer PD-84 (manufactured by Konica Corp.) to obtain green densities DG of 0.5 and 1.5. DB / DG when
(DG is blue density) was evaluated.

The concentration ratio of DG = 0.5 to 1.5 is 0.35 to 0.
55 is more preferable, and the difference between the ratio of DG = 0.5 and the ratio of 1.5 is preferably 0.15 or less, more preferably 0.10.
It is the following.

The coupler used in the silver halide light-sensitive material of the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound to be obtained can be used, as a typical example, a yellow coupler having a spectral absorption maximum in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range of 600 The one known as a cyan coupler having a spectral absorption maximum wavelength at ˜750 nm is typical.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
JP-A-4-114154, the general formula (C
Examples thereof include couplers represented by -I) and (C-II). Specific compounds include those described as CC-1 to CC-9 in the same publication, page 5, lower right column to page 6, upper left column.

A magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (MI) described in JP-A-4-114154, page 4, upper right column. A coupler can be mentioned.
Specific compounds are described in MC in page 5, upper left column to same, upper right column.
-1 to MC-7 can be mentioned.

The yellow coupler of the yellow color-developing blue light-sensitive layer which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is described in JP-A-4-114154, page 3, upper right column (Y-I). ) And a coupler represented by Specific compounds include those described as YC-1 to YC-9 in the same publication, page 3, lower left column to page 4, upper left column. Among them, YC-8 and YC-9 described in the upper left column of page 4 of the same publication are preferable because they can reproduce a preferable yellow color.

As the yellow coupler to be added to the magenta color-developing green photosensitive layer or another layer, in addition to the above yellow coupler, JP-A-2-139542, page 13, upper left column to 17th page
Examples thereof include those described as Y-1 to Y-58 described in the lower left column of the page.

Specific examples of the yellow coupler to be added to the magenta coloring green photosensitive layer in the present invention are shown below.

[0025]

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[0026]

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[0027]

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[0028]

[Chemical 4]

[0029]

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[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

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[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. 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 the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added.

As the high boiling point organic solvent which can be used for dissolving and dispersing the coupler (and a photographically useful organic compound such as an ultraviolet absorber and a color turbidity preventing agent described later), 10
A high boiling organic solvent having a vapor pressure of 0.5 mmHg or less at 0 ° C. is preferable. Specific examples of the compounds include compound examples II-1 to II-9 and III-1 to III-6 described in JP-A-63-103245, and compound examples H-1 to H-22 described in JP-A 1-196048. , JP Sho
Examples of compounds II-1 to II-38 described in 64-66646 or phosphine oxides as shown below are mentioned. Phosphate esters such as tricresyl phosphate and phosphine oxides are preferably used. Specific examples of the phosphine oxides include those having the following structures.

[0040]

Embedded image

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt-
Butyl acrylamide) and the like.

Ethyl acetate is preferably used as the low boiling point organic solvent. In addition, as a preferred surfactant used at the time of dispersion, a hydrophobic group having 8 to 30 carbon atoms in one molecule and -SO ₃ M group or -OSO ₃ M (M represents a hydrogen atom or a cation) The compound which has both can be mentioned. Specific examples of preferable surfactants include anionic surfactants A-1 to A-11 described in JP-A 64-26854, page 15, upper left column to upper right column, more preferably A-11 and A-11. A-8 is mentioned. Further, a surfactant having a fluorine atom substituted in the alkyl chain is also preferably used.

It is also preferable to add these surfactants to the coating liquid. These dispersions are usually added to a coating solution containing a silver halide emulsion and then coated, but it is preferable that the dispersion is added to the coating solution within 10 hours, more preferably within 3 hours, most preferably 20 minutes. Is to be added within.

For the purpose of shifting the absorption wavelength of the color-forming dye, the compound (d-
11), compounds such as the compound (A'-1) described on page 35 of the same publication can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compounds described in 774,187 can also be used.

[0045] The coating amount of the coupler, if it is possible to obtain a sufficiently high concentration is not particularly limited, preferably 1 mol of silver halide per 1 × 10 ^-3 to 5 mol, more preferably 1 × 10 ^- It is used in the range of ² to 1 mol.

An anti-fading agent may be used in combination with the magenta coupler used in the present invention. As the first of this compound,
Examples thereof include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, upper left column to upper right column. Specific examples of compounds include compounds I-1 to I-32 and II-1 to 1-lower right column on page 3 to 5-upper right column of the same publication.
II-18 can be mentioned. Of these, more preferred compounds are I
It is a compound represented by -13 and II-9.

The second anti-fading agent preferably used in combination is a phenolic compound represented by the general formula IIIB described in JP-A-3-174150. Of these, the compounds III-1, III-12, III-13, and III-14 described in the above publication are more preferable, and the compound represented by III-14 is particularly preferable.

The third type of anti-fading agent preferably used in combination is an amine compound represented by the general formula A shown in JP-A No. 64-90445. Specific examples of compounds include A-1 to A-15 described in the upper right column of the same publication.
Of these, the more preferred compound is A-3.

An anti-fading agent is preferably used in combination with the yellow coupler and the cyan coupler according to the present invention. Among them, preferred anti-fading agents include compounds represented by the general formula I'in the left upper column of JP-A 1-196049, page 8 and compounds described in JP-A-5-11417. More preferable compounds are the compounds represented by I-10 and I-13 described in JP-A 1-196049, page 9, upper left column to upper right column. The anti-fading agent used in combination with these magenta, yellow and cyan couplers is preferably added in the same oil oil droplet as the coupler at a ratio of 0.1 to 3 mol, and more preferably 0.5 to 1.5 mol, per mol of the coupler. More preferably, it is added in a ratio of. As the anti-fading agent, it is preferable to use different compounds in combination, and the phenolic compound represented by the general formula IIIB described in JP-A-3-17450 and the general formulas I and II described in JP-A-2-66541, page 3, upper right column. A preferred example is the combined use of a phenyl ether compound represented by Further, a combined use of the phenolic compound represented by the general formula IIIB described in JP-A No. 3-17450 and the amine compound represented by the general formula A described in JP-A No. 64-90445 is also a preferable combination example.

Examples of the ultraviolet absorber used in the present invention include compounds having a spectral absorption maximum wavelength in the ultraviolet region (400 nm or less) and a molecular extinction coefficient of 5000 or more. Examples of preferred compounds include the compounds represented by the general formula III-3 described in JP-A 1-250944 and the compounds represented by the general formula I described in JP-A 4-1633. Specific examples of compounds include IIIc-1 to IIIc-1 described in JP-A 1-250944.
7, III-1 to III-24 and 63-18 described in JP-A-64-66646
UV-1L to UV-22L described in 7240, U described in the same publication
V-1S to UV-19S and compounds described in JP-A-4-1633
Examples thereof include I-1 to I-23. Among them, particularly preferable compounds are described in JP-A 1-250944, page 15, upper left column.
IIIc-7 and IIIc-12, and the liquid ultraviolet absorber UV-23L described in JP-A-63-187240. These UV absorbers are preferably added by the above dispersion method, but in the present invention, the high boiling point organic solvent used in the UV absorber layer is 0.3 to 0 in weight ratio to the UV absorber.
Is added in the ratio of. The ratio is preferably 0.1 to 0, and most preferably 0. As the high boiling point organic solvent, the compound used for dispersing the coupler is preferably used. In the present invention, the ultraviolet absorber is preferably contained in the non-photosensitive layer. Further, it is separated from the non-photosensitive intermediate layer further apart from the silver halide emulsion layer farthest from the support and the emulsion layer farthest away from the support, and second away from the emulsion layer. It is a light-insensitive layer intermediate to the emulsion layer in position.

In the present invention, it is preferable to add fine particle powder (so-called matting agent) to the surface layer and the layer farthest from the support. As a matting agent, JP-A-2-7325
The compounds described in No. 0, page 2, upper right column, lines 9 to 20 are preferred, and crystalline or amorphous silica is most preferred.
These may be used alone or in combination of two or more. The average particle size of the matting agent is 1 to
10 μm is preferable, and 2 to 7 μm is more preferable. The coating amount of the matting agent is 0.021 to 0.1 g / m ² , and more preferably
It is 0.025 to 0.08 g / m ² .

It is also preferable to add a high boiling point organic solvent to the surface layer. As a preferable high boiling point organic solvent to be added to the surface layer, a high boiling point organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less is preferable, and a compound having a dielectric constant of 6.0 or less is more preferable. As specific examples of compounds, those described in the dispersion of the coupler can be mentioned as they are. The addition amount is 1 to 100 mg / m ² , preferably 10 to 50 mg / m ² .

To the light-sensitive material according to the present invention, a fluorine-containing surfactant or an organopolysiloxane is added for the purpose of improving surface properties such as glossiness, stickiness, sticking resistance, slipperiness and scratch resistance. You may. Preferred fluorine-containing surfactants include compounds represented by the general formulas (I), (II) and (III) described in JP-A-6-118543. Among them, particularly preferred are FI-55, FI-81, FK-
5, FK-13 and FK-23. Preferable organopolysiloxanes include compounds represented by formulas (S1), (S2), (I), (II) and (III) described in JP-A-6-118543. Among them, particularly preferable compounds include the compounds represented by S-7 and S-19.

In the present invention, it is preferable to use an oil-soluble dye. An oil-soluble dye has a solubility in water at 20 ° C of 0.01
The following organic dyes are referred to, and compounds having a molecular absorption coefficient of 20,000 or more at the maximum absorption wavelength at a wavelength of 400 nm or more are preferable. Preferred compounds include JP-A-2-842, page 7, lower right column to 8
The compounds of the general formulas II and III shown in the upper left column of the page are mentioned. Examples of preferable specific compounds include compounds 1 to 27 described in the same publication, page 8, lower left column to page 9, upper right column.
Of these, compounds 4 and 9 are particularly preferable. The oil-soluble dye is preferably added to the non-photosensitive layer, and 0.05 to 5 mg / m ²
Is preferably added in an amount of.

In the present invention, it is preferable to add a fluorescent whitening agent to the light-sensitive material. As a fluorescent whitening agent, JP-A-2-
A compound represented by the general formula II described in No. 232652 is preferable,
Specific examples of compounds include compounds 1 to 6 described in the lower right column on page 6 to the upper right column on page 7 of the same publication. Of these compounds
The compounds shown in Nos. 3, 1 and 5 are particularly preferable. These optical brighteners are preferably added to the non-photosensitive layer. Preferably 0.001~0.3mg / m ² as amount, even more preferably 0.1 to 0.2 mg / m ^2.

In the present invention, it is preferable to add a water-soluble polymer compound which complements the above-mentioned optical brightening agent and enhances the optical brightening effect. Preferred compounds include polyvinylpyrrolidone and polymers containing vinylpyrrolidone as a repeating unit. These are preferably contained in the ultraviolet absorber-containing layer farthest from the support and / or in a layer further distant from the layer.

For the color light-sensitive material of the present invention, it is preferable to use water-soluble dyes having absorption in various wavelength regions for the purpose of preventing irradiation and halation.
As a preferable anti-irradiation dye, JP-A-62-62
Of the general formula II described in JP-A-253146 (as specific examples of compounds, compounds II-1 to II-19 described in page 12, upper left column to page 13, lower left column), JP-A 64-26850 General formula of
Compounds represented by I (for specific compound examples, the publication 7
Compounds Nos. 1 to 85 described in the upper left column of the page to the lower right column of the page 11) and compounds represented by the general formula I described in JP-A-2-97940 (specific examples of the compound, page 5, lower column of the same publication-9). At the top of the page
Nos. 1 to 103), JP-A-6-3770, page 4,
The compounds described on page 5 can be mentioned. Of these, particularly preferred compounds include compound No. 47 represented by general formula I described in JP-A No. 64-26850, compound No. 54 represented by general formula I described in JP-A No. 2-97940, 1, Kaihei 6-3770 description
It is a compound represented by 4, 6, 7, and 9.

As the anti-irradiation dye, it is preferable to use a dye having different maximum absorption wavelengths in combination, and 600 to 7
It is preferable to use a dye having a maximum absorption at 00 nm, a dye having a maximum absorption wavelength at 500 to 600 nm, and a dye having a maximum absorption wavelength at 400 to 500 nm in combination. These dyes may be added to any layer, but are preferably added to the non-photosensitive layer. The addition amount is preferably 1 to 100 mg / m ² for each compound.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The form of reacting the soluble silver salt and the soluble halide is a forward mixing method, a reverse mixing method, a simultaneous mixing method,
Any combination thereof may be used, but those obtained by the simultaneous mixing method are preferable. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor as described in JP-A-57-92523 and 57-92524, German Published Patent 2921164, etc., a device for continuously changing the concentration of water-soluble silver salt and water-soluble halide aqueous solution, and the reaction mother liquor taken out of the reactor as described in JP-B-56-501776 You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by a filtration method.

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 during the formation of silver halide grains or after the completion of grain formation. In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be left as it is. The removal of the salts can be carried out according to the method described in Research Disclosure 17643.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. or,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26589
Issue, Japanese Examined Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) Volume 21
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron are prepared by the method described in the literature such as page 39 (1973),
It can also be used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape or a mixture of grains having various shapes.

The grain size of the silver halide grain is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.6 μm, more preferably 0.2 to 1.2.
It is in the μm range. The particles can be measured by various methods generally used in the technical field. The particle size can be obtained by using the projected area of the particle or an approximate diameter value.

If the particles are of substantially uniform shape,
The particle distribution can be represented fairly accurately using diameter or projected area. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Monodispersed silver halide having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain distribution of silver halide grains is preferable. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following. Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains, or In the case of particles having a shape other than a cube or a sphere, the projected image represents the diameter when converted into a circular image having the same area.

The silver halide grain emulsion according to the present invention is silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver bromide or silver chloride, but preferably substantially contains silver iodide. Not more than 80 mol% is silver chlorobromide grains or silver chloride consisting of silver chloride. The content of substantially no silver iodide means that the silver iodide content is 0.
It is 5 mol% or less, preferably 0.1 mol% or less, more preferably not contained at all. The silver chloride content is preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more.

When the silver halide grains according to the present invention are silver chlorobromide containing silver bromide, core / shell grains having a different composition within the silver halide grains or a silver bromide localized phase are provided on the grain surface. Alternatively, the grains may be inside, but silver halide grains having a uniform composition from the inside to the surface are preferable.

The silver halide emulsion according to the present invention contains various metal salts in the course of grain formation or physical ripening, or
A metal complex salt can be introduced.

The metal used is the first in the periodic law.
VIB group, VIIB group, VIII group, IIB group, IIIA group,
Group IVA can be mentioned, and among them, those preferably used are Mn, Fe, Co, Ni, Zn, Ga, Ge, Mo, Ru, Pd, C.
It is a salt or complex salt of d, In, Sn, W, Re, Os, Ir, Pt, Tl, Zn, Au. These may be used alone or in combination.
Preferred metal salts or complex salts are Japanese Patent Application Nos. 2-162332 and 2-25.
No. 3667, No. 3-109173, No. 4-251468, No. 4-82250,
It is described in JP-A-4-125629, JP-A-4-251469, JP-A-4-253081 and the like.

The amount of these compounds added varies over a wide range depending on the kind of the compound or the purpose.
10 ^-11 to 10 ^-3 mol is preferably used with respect to the mol.

The silver halide grain emulsion according to the present invention can be used in combination with a gold sensitizing method using a gold compound and a (sulfur) sensitizing method using a chalcogen sensitizer.

As the gold sensitizer, chloroauric acid, gold chloride, gold thiosulfate, and various other gold complexes can be added. Examples of the oxidizing compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The amount of the gold sensitizer used varies depending on the type of silver halide emulsion, the type of gold compound, the ripening conditions, etc., but is usually 1 × 10 ^-9 to 1 × per mol of silver halide.
10 ⁻⁴ mol is preferable, and more preferably 1 × 10 ⁻⁸ to 1 × 10 5.
^-5 mol.

As the chalcogen sensitizer, a sulfur sensitizer,
Although a selenium sensitizer and a tellurium sensitizer can be used,
Sulfur sensitizers are preferred. Examples of the sulfur compound include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenesulfonate, rhodanine, and inorganic sulfur.

The light-sensitive material of the present invention can be subjected to reduction sensitization. Known methods are known for reduction sensitization. For example, a method of adding various reducing agents, a method of aging under conditions of high silver ion concentration, a method of aging under conditions of high pH, and the like can be used.

Examples of the reducing agent used for reduction sensitization include stannous salts such as stannous chloride, boranes such as tri-t-butylamine borane, sulfites such as sodium sulfite and potassium sulfite, and reductones such as ascorbic acid. Examples thereof include thiourea dioxide and the like. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents may be dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or may be added during the formation of silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents added needs to be adjusted depending on the pH of the silver halide emulsion, the silver ion concentration, etc.
It is preferably 10 ⁻⁷ to 10 ⁻² mol.

After the reduction sensitization, a small amount of an oxidizing agent may be used for modifying the reduction sensitizing nucleus or deactivating the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, thiosulfinic acid, and hydrogen peroxide solution.

A silver halide solvent may be added to the silver halide emulsion according to the present invention in the process of sensitization. The silver halide solvent preferably used is thiocyan compounds, and examples thereof include potassium thiocyanate, sodium thiocyanate, calcium thiocyanate, magnesium thiocyanate, silver thiocyanate and ammonium thiocyanate.

The pH and pAg at the time of sensitization are not particularly limited, and are usually
It is performed in the range of pH 4.0 to 11.0 and pHAg 4.5 to 8.5.

The silver halide emulsion according to the present invention has a known fog for the purpose of preventing fog during the process of preparing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog during development. Inhibitors and stabilizers can be used. Examples of compounds used for such purpose include compounds represented by the following general formula [S].

[0085]

[Chemical 15]

In the formula, Q represents a group of non-metal atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or an alkali metal atom.

The 5-membered heterocyclic ring represented by Q is, for example, imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzimidazole ring,
A naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring and the like can be mentioned. The 6-membered heterocyclic ring represented by Q includes a pyridine ring, a pyrimidine ring,
Examples thereof include a quinoline ring, and these 5- or 6-membered heterocycles include those having a substituent. Examples of the alkali metal atom represented by M include a sodium atom and a potassium atom.

A more preferred structure of the mercapto compound represented by the general formula [S] is described in JP-A-6-175263, page 3, right column to 4
As described in the right column of the page. Further, specific compounds include S-1-1 to S-S described on pages 5 to 10 of the publication.
-4-8 can be mentioned. Further, the compound represented by the general formula [I] of JP-A No. 5-218683 is also preferable, and specific examples thereof are 1 to 49 in the left column on pages 4 to 6 of the publication.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention. As a blue-sensitive sensitizing dye, JP-A-3-2518
BS-1 to 8 described in No. 40, page 28, upper right column to page 28, lower left column can be preferably used alone or in combination.
Examples of the green-sensitizing sensitizing dye include G described in the lower right column of the publication.
S-1 to 5 are preferably used.

When the light-sensitive material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, Kahei 4-285950 I described on pages 6-8
The dyes RS-1 to 11 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes.

When the light-sensitive material according to the present invention is exposed using a laser, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the luminous flux in the case of scanning exposure with laser light. In the spatial variation of the intensity of the light, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value, the line parallel to the scanning line and passing through the point where the light intensity is maximum and the outer edge of the light flux. When the distance between two intersecting points is the ray of the light beam, it can be considered as the exposure time per pixel by (the ray of light beam) / (scanning speed). As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-407.
1, 59-11062, 63-197947, JP-A-2-74942
No. 2-236538, Japanese Patent Publication No. 56-14963, No. 56-40822,
European Wide Area Patent 77410, Technical Report of Department of Electronic Communication 80
Volume 244 and movie television technical magazine 1984/6 (382) pages 34-36.

Cyanine dyes represented by the following general formulas [2] and [3] are preferably used as the red-sensitive sensitizing dye.

[0094]

Embedded image

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an alkenyl group or an aryl group. L ₁ ,
L ₂ , L ₃ , L ₄ and L ₅ each represent a methyl group. Z ₁ ,
Z ₂ , Z ₃ and Z ₄ each represent an atom or a group of atoms necessary for completing a 5- or 6-membered heterocyclic nucleus. Z ₅ represents an atomic group necessary for forming a 6-membered carbocycle. m ₁ , m ₂ , m ₃ and m ₄ each represent 0 or 1. n represents 0 or 1. X ^-
Represents an acid anion. Y ₁ and Y ₂ each represent 0 or 1, and when the compound forms an intramolecular salt, Y ₁ and Y ₂ are
Each represents 0.

Examples of the supersensitizer used in the silver halide emulsion according to the present invention include stilbene, azaindene,
A compound such as a mercapto heterocyclic compound or a condensate of thiourea or phenol and hexamethylenetetramine can be used, but it is preferable to use a 9-membered or more cyclic compound containing a heterocycle.

The cyclic compound is preferably one having an aliphatic ring and / or an aromatic ring and an ether bond from the viewpoint of effect, and the aliphatic ring forming the cyclic compound is preferably 4 or less, and has an aromatic ring. Macrocyclic compounds are more preferred.

Representative compounds are crown ethers, and specific examples of these cyclic compounds include S-1 to S-39 described on pages 11 to 17 of JP-A-6-175263.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder for dispersion and for coating liquid.

For the production method of gelatin, for example, TH Jame
s; The Theory of The Photographic Process, 4th ed. (19
77) page 55 and the basics of photographic engineering, silver halide photography, pages 119 to 124. As the raw material, cow bone (ossein) cowhide (hide) and pig skin (pig skin) are used, preferably prepared from cow bone, but even if two or more kinds of them are mixed, Good.

As the treatment, alkali treatment, acid treatment, oxygen treatment and the like are carried out, but alkali-treated gelatin is preferred. The isoelectric point of the alkali-processed gelatin is preferably 4.5 or higher, more preferably 5 or higher. Although gelatin can be usually subjected to ion exchange treatment, in the present invention, cation, anion and gelatin subjected to both ion exchange treatment can be appropriately selected depending on the use, but gelatin subjected to both ion exchange is preferred. Gelatin treated with hydrogen peroxide is also preferably used.

The hydrogen peroxide treatment may be performed in any of the gelatin preparation steps. For example, it may be performed directly on ossein, during the alkali treatment, after the alkali treatment, or after extraction as a gelatin solution. In the present invention, gelatin prepared by adding hydrogen peroxide solution during alkali treatment is preferable. Hydrogen peroxide is added in the range of 1 to 100 g as pure H ₂ O ₂ per 1 kg of ossein. The reaction with hydrogen peroxide is preferably carried out at a pH of 9.0 or higher.

The composition of gelatin is preferably such that the low molecular weight component is small and the high molecular weight component is large. For the measurement method of high and low molecular weight components, see JP-A 1-265247.
The method described on page 2, lower left column, line 15 to page 3, upper left column, line 8 can be used. It is more preferable that the high-molecular weight component is 30% or more and / or the low-molecular weight component is 40% or less, according to the method. The molecular weight of gelatin is preferably 10,000 to 200,000.

The jelly strength of gelatin is preferably high, and more preferably 250 or more. Particularly preferred is 270 or more.

The content of ions as impurities contained in gelatin is preferably as low as possible. For example, the calcium ion content is preferably 5000 ppm or less, more preferably 2000 ppm or less. However, depending on the emulsion, the presence of 4000 to 5000 ppm of calcium may be preferable.

Heavy metal ions such as iron and copper ions are preferably 500 ppm or less in total and 10 ppm or less in each component. In particular, the iron ion content is 5 ppm or less, more preferably 3 ppm or less.

Further, the higher the specific optical rotation of gelatin is, the more preferable it is, and the more preferable value is 150 or more. When used for the top layer,
A specific rotation of 210 or more is preferable.

The less the coloring of gelatin is, the better the gelatin is. The transmittance of a 10% by weight aqueous solution of gelatin at 420 nm is 50%.
Above, preferably 60% or more, more preferably 70% or more gelatin is advantageous for the present invention. In order to increase the transmittance of gelatin, selection of raw materials, hydrogen peroxide treatment, ion exchange, adsorption with a chelate resin, etc. are appropriately performed.

The total amount of gelatin contained in the light-sensitive material of the present invention is 10.0 g / m ² or less, preferably 7.0 g / m ² or less. The lower limit is not limited, but it is generally from the viewpoint of physical properties or photographic performance. It is preferably 3.0 g / m ² or more.
The amount of gelatin is determined by the water content measurement method described in the Pagui method.
It is calculated in terms of the weight of gelatin containing 11.0% water.

In the present invention, a binder hardener is used. As the hardener, vinyl sulfone type hardeners and chlorotriazine type hardeners are preferably used. As the vinyl sulfone type hardener, compounds described in JP-A No. 61-249054, page 25, upper right column, line 13 to page 27, upper right column, line 2 can be preferably used. Further, the compound H-12 described on page 26 of the same publication is more preferable. Examples of the chlorotriazine-based hardener include JP-A-61-245153, page 3, lower left column, line 1 to page 3, lower right column, line 4 to lower, and page 3 lower right column, lower line 4 to page 5, lower left column. The compounds mentioned are preferably used. Further, the compound represented by XII-1 described on page 4 of the same publication is more preferable.
These hardeners are preferably used in combination with different compounds, and may be added to any layer. The hardener is preferably used in an amount of 0.1 to 10% by weight based on the binder.

In the present invention, it is preferable to add a mildew proofing agent to either layer. Preferred compounds include
The compound represented by the general formula II described in JP-A-3-157646, page 3, lower left column is preferable. Specific examples of compounds include the same publication
Compound Examples Nos. 9 to 22 described in the upper left column on page 19 to the upper right column on page 19 are mentioned. Of these, the compound shown as No. 9 is particularly preferable. In the present invention, a preservative and a fungicide can be used. Preferred examples are the compounds described in JP-A-3-157646, page 17, lower right column, line 16 to page 19, lower left column.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, fine silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, oxidation Examples thereof include zinc, talc, and clay, but barium sulfate and titanium oxide are preferable. The white pigment may be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight, as the content in the waterproof resin layer.
It is preferably not less than 15% by weight, more preferably not less than 15% by weight. The dispersity of the white pigment in the waterproof resin layer of the paper support is
It 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, more preferably 0.15 or less, and further preferably 0.10 or less as the coefficient of variation described in the above publication. The surface of the paper support is preferably smoother, and the central average roughness (SRa) is 1.0 μm.
The following is preferred. The calculation method of SRa is Japanese Patent Application No. 3-2.
Calculated by the formula described on page 6 of No. 576.

The base paper used for the support of the present invention is selected from commonly used materials. That is, bleached softwood pulp by sulfuric acid method (NBKP), bleached hardwood pulp by sulfuric acid method (LBK)
P), sulfite bleached softwood pulp (NBSP), sulfite bleached hardwood pulp (LBSP), and other natural pulps may be used alone or in combination of two or more. When used in combination, the desirable pulp mixture ratio is hardwood pulp /
The ratio of softwood pulp is 95/5 to 60/40.

In the present invention, it is preferable to add various additives shown below to the base paper to enhance paper strength such as water resistance. For example, as a sizing agent, alkyl ketene dimer fatty acid salt, rosin, maleated rosin, alkenyl succinate,
Alkyl succinate and polysaccharides are used, but alkyl ketene dimer fatty acid salt is preferably used. It is preferable to use 0.2 to 2% of these per pulp. As the dry paper strengthening agent, cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol and the like are used, but cationized starch and anionized polyacrylamide are preferable. Further, as the wet paper strength enhancer, melamine resin, urea resin, epoxidized polyamide resin and the like are used, but epoxidized polyamide resin is preferable. Also, generally, the surface of the pulp is tab-sized or size-pressed with a liquid containing a water-soluble polymer additive. As the water-soluble polymer, cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, gelatin and the like can be used, but cationized starch and polyvinyl alcohol are preferable.

As an antifoggant, there is disclosed in JP-A-55-103549.
Water-soluble iodine compounds described in JP-A No. 56-43637, weak acid salts or oxides of magnesium, calcium or zinc described in JP-A-56-43637, urea compounds having a molecular weight of 150 or less described in JP-A-56-97343, The magnesium compounds described in 19405 are used. Of these compounds, magnesium hydroxide, magnesium oxide, calcium oxide, and zinc oxide are preferable, and are used in an amount of 0.1 to 10% by weight based on the pulp. Further, as the inorganic electrolyte, salt, mirabilite or the like is used, but salt is preferable. Glucerin, polyethylene glycol, etc. are used as the hygroscopic substance, hydrochloric acid, sodium hydroxide, sodium carbonate, etc. are used as the pH adjuster, and other dyes (blue dye, ultramarine blue are preferable), fluorescent whitening agents, antistatic agents, decolorizing agents, etc. Additives such as foaming agents are used in combination. After the pulp is appropriately crushed, it becomes a pulp slurry containing the above additives as required, and is made into paper by a paper machine such as a Fourdrinier paper machine and dried and supercalendered. Surface sizing is performed before or after this drying.

The support is preferably a base paper obtained as described above, coated on both sides with a polyolefin resin. Examples of the polyolefin resin include polyethylene,
Homopolymers of α-olefins such as polypropylene and mixtures of these polymers, and particularly preferred polyolefins are high-density polyethylene, low-density polyethylene or a mixture thereof. The molecular weight of these polyolefins is not particularly limited, but polyolefins in the range of 20,000 to 200,000 are generally used. There is also no particular limitation on the thickness of the polyolefin resin coating layer, and usually about 15 to
It is 50 μm thick. When the support is a paper support, various forms of support can be used. For example, a thin base paper having a support thickness of 80 to 180 μm, a release described in Japanese Utility Model Application No. 64-29550, etc. Adhesive and thick base paper can also be used. When a support such as polypropylene or polyethylene terephthalate is used, it can be produced by adjusting the amount of white pigment applied to each of transparent, translucent and opaque types. The oxygen permeability of the support is preferably 2.0 cc / m ² · hr · atm or less.

As a reflective support according to the present invention, a photographic paper support having a resin composition layer containing an inorganic and / or organic white pigment and cured by electron beam irradiation on at least one side of a substrate is also highly smooth. It has high sharpness and is preferably used.

The electron beam curable coating liquid used in the present invention contains at least one organic compound capable of forming a cured resin by an electron beam and a pigment, preferably an inorganic pigment, as main components, and if necessary, other additives are added. It contains an agent.

Organic compounds which are polymerized and cured by electron beam irradiation are unsaturated compounds containing two or more carbon-carbon double bonds in one molecule, such as acrylic and methacrylic oligomers, polyfunctional acrylic and methacrylic compounds. Monomers and unsaturated compounds containing at least one carbon-carbon double bond in one molecule, such as monofunctional acrylic monomers, methacrylic monomers and vinyl monomers are included.

These unsaturated organic compounds generate radicals by electron beam irradiation to polymerize, and form crosslinks due to intermolecular and intramolecular crosslinking reactions to be cured to form a cured resin.

Typical resins have acryloyl and methacryloyl groups at both ends and have a skeleton of polyester,
There are compounds that are polyurethanes, polyethers and polycarbonates.

The acrylic and methacrylic oligomers include acrylic acid or methacrylic acid ester of polyurethane, acrylic acid or methacrylic acid ester of polyether alcohol, acrylic acid or methacrylic acid ester of bisphenol A, maleic acid or fumaric acid ester of polyester. And so on. Further, as the polyfunctional acrylic monomer and methacrylic monomer, 1,6-hexanediol diacrylate, neopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, glycerol trimethacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol pentaacrylate, neopentyl glycol diacrylate, isocyanamic acid diacrylate, isocyanamic acid triacrylate, trimethylolpropane triacrylate Acrylate, propylene oxide modified trimethylo , And the like Le propane polyacrylate. In addition, monofunctional acrylic monomer,
As the methacrylic monomer and the vinyl monomer, methyl acrylate, ethyl acrylate, butoxyethyl acrylate, benzyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, phenoxyethyl acrylate, N, N-diethylaminoethyl methacrylate,
Examples thereof include styrene, N-vinylpyrrolidone, polyoxyethylenephenol acrylic acid ester, and 2-ethylhexyl acrylate.

As commercially available products, for example, Aronix M-5700 and M-6100 (polyester acrylate), Aronix M-1100 and M-
1200 (urethane acrylate), Aronix M-10
1,102 (monofunctional acrylate), Aronix M-21
Examples thereof include 0, 215 (multifunctional acrylate, all manufactured by Toa Gosei Co., Ltd.) and GE-510 (epoxy compound: manufactured by Mitsubishi Gas Co., Ltd.).

The coating liquid contains a pigment, usually a white inorganic pigment, uniformly mixed with an electron beam-curable organic compound dissolved or dispersed in an organic solvent. As the white inorganic pigment, the white pigment used for the reflection support can be used as it is.

The content of the white inorganic pigment in the coating solution is preferably set to 20 to 80% by weight based on the total solid weight of the cured resin coating layer. When the content is less than 20% by weight, the sharpness of the obtained photographic image on the photographic paper is not sufficient, and when the content exceeds 80% by weight, the flexibility of the obtained cured resin coating layer is deteriorated. , Film cracks will occur. To disperse the white inorganic pigment in the electron beam curable unsaturated organic compound, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill),
Cowles dissolver, homomixer, sand grinder, ultrasonic disperser, etc. can be used.

As the organic solvent, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ether, glycol monoethyl ether, dioxane, benzene, toluene, xylene, ethylene chloride, carbon tetrachloride, chloroform, dichlorobenzene or the like can be used. .

As a coating method, a roller coating method may be used, or alternatively, a general method used for coating a sheet, for example, a bar coating method, an air doctor coating method, a blade coating method, a squeeze coating method. Any of an air knife coating method, a reverse roll coating method, a transfer coating method and the like may be used. A fountain coater or slit orifice coater system can also be used.

The electron beam irradiation apparatus used in the present invention is not particularly limited, and generally, as such an electron beam accelerator for electron beam irradiation, a curtain beam type which is relatively inexpensive and can obtain a large output is used. Used effectively. The acceleration voltage during electron beam irradiation is preferably 100 to 300 kV, and the absorbed dose is preferably 0.5 to 10 Mrad.

The thickness of the coating layer is 3 to 100 μm, preferably 5 to 50 μm. If the amount is out of this range, coating unevenness occurs, a large amount of energy is required for curing, and curing becomes insufficient, which is not preferable in terms of quality.

If necessary, the surface of the coating solution may be smoothed with a mirror-finished roll or cured, or the surface may be matted with a matte roll such as a silk roll.

As the support substrate used in the present invention,
Generally, any material used for a photographic support can be used, but paper is usually used. Examples of the paper used as the sheet substrate include natural pulp paper, synthetic pulp paper, mixed paper of natural pulp and synthetic pulp, and various types of combined paper. These paper substrates may be blended with additives such as sizing agents, paper strengthening agents, fixing agents, fillers, antistatic agents, pH adjusting agents, pigments and dyes which are generally used in papermaking. . Further, a surface sizing agent, a surface paper strength agent, or an antistatic agent may be applied on the surface.

The light-sensitive material according to the present invention may be directly or undercoated (adhesiveness, antistatic property on the surface of the support) after corona discharge, ultraviolet irradiation, flame treatment, etc. It may be applied via one or more undercoat layers) to improve dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties. When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability.
As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The prepared light-sensitive material is exposed on the basis of halftone dot information consisting of color-separated yellow image information, magenta image information, cyan image information and black image information.
The exposure may be performed in close contact with the halftone dot original film, or may be performed using a laser printer device or the like based on digitized halftone dot information.

In the present invention, the time from exposure to development may be any time, but a shorter time is preferred in order to shorten the overall processing time. Further, the light-sensitive material according to the present invention has a small change in image density even when the time from exposure to development is 30 seconds or less, and a high quality image can be stably obtained.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. Representative compound examples are shown below.

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-hydroxyethylamino)
Aniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethylamino) aniline CD-6: 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl ) 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- (β-Butoxyethyl) aniline CD-12: 4- (N-ethyl-N- (β-hydroxypropylamino) aniline These color developing agents may be used alone or in the known p-phenylenediamine. You may use together with a derivative.

The color developing agent is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the developing solution, and from the viewpoint of rapid processing, it is 1.5 × 10 2 per liter of the color developing solution.
It is preferably used in the range of ^{−2 to} 2 × 10 ⁻¹ mol.

The color developing agents used in the present invention are preferably CD-5, CD-6 and CD-9. In particular, CD-5 is preferable in order to bring it closer to the color tone of the printing ink. These p-phenylenediamine derivatives are generally used in the form of salts such as sulfate, hydrochloride, sulfite, nitrate and p-toluenesulfonate.

The preferred developer of the present invention preferably contains substantially no benzyl alcohol. Here, the term "substantially free" means that benzyl alcohol is 2 cc / liter or less, and it is most preferred that the present invention does not include benzyl alcohol at all.

The color developer may contain the following developer components in addition to the above components. As an alkaline agent,
For example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicate or the like may be used alone or in combination to maintain the pH stabilizing effect without causing precipitation. It can be used in combination within the range. Furthermore, because of the necessity of preparation,
Alternatively, for the purpose of increasing ionic strength, hydrogen phosphate 2
Sodium, dipotassium hydrogen phosphate, sodium bicarbonate,
Various salts such as potassium bicarbonate and borate can be used.

In the present invention, it is preferable that the color developing solution contains chlorine ions in an amount of 2.5 × 10 ^{-2 to} 5 × 10 ^-1 mol / liter. In addition, bromide ion is 2.0 × 10 ^-5 ~ 2.0
It is preferable to contain ^{x10 -2} mol / liter.

Here, the chlorine ion and the bromine ion may be added directly to the developing solution, or may be eluted from the light-sensitive material into the developing solution during the development processing. When directly added to the color developer, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, cadmium chloride and the like can be mentioned as a chloride ion supplying substance, but preferred ones among them. Are sodium chloride and potassium chloride.
Further, it may be supplied from an optical brightener added to the developing solution.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, as a bromine ion-supplying substance,
Examples thereof include nickel bromide, magnesium bromide, manganese bromide, calcium bromide, cadmium bromide, cerium bromide, thallium bromide and the like, among which sodium bromide and potassium bromide are preferable. When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

Further, in the color developing solution, instead of hydroxylamine which has been conventionally used as a preservative, JP-A-63-1 is used.
46043, 63-146042, 63-146041, 63-146040
No. 63-135938, No. 63-118748, and No. 63-179351.
And hydroxylamine derivatives described in JP-A-64-6
2639 and JP-A-1-303438, etc., hydroxamic acids, hydrazines, hydrazides, phenols, α-
Preferred as organic preservatives are hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed amines. Used.

These compounds may be used in combination with the conventionally used hydroxylamine and the above organic preservatives, but it is preferable not to use hydroxylamine from the viewpoint of developing characteristics.

If necessary, a development accelerator can be used. Examples of the development accelerator include U.S. Pat.
No. 4, 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. Issue 2,53
1,832, 2,950,970, 2,577,127 and JP-B-44-
Polyethylene glycol and its derivatives described in 9504, nonionic compounds such as polythioethers, JP-B-44-950
Organic solvents and organic amines described in No. 9, ethanolamine,
Examples include ethylenediamine, diethanolamine, triethanolamine and the like. Further, phenethyl alcohol described in U.S. Pat. No. 2,304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

If necessary, ethylene glycol,
Methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, p-toluenesulfonic acid, and other compounds described in JP-B-47-33378 and 44-9509 are dissolved aids for increasing the solubility of the developing agent. It can be used as an agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of the auxiliary developer include N-methyl
-p-aminophenol sulfate, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride, etc. are known,
The amount added is usually 0 per liter of developer.
01 to 1.0 g is used. In addition to these, competitive couplers, fogging agents, development inhibitor releasing couplers (D
IR couplers), development inhibitor releasing compounds and the like can be added.

Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. in this case,
The component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution may be prepared by adding a plurality of components which can coexist stably in a concentrated aqueous solution, or a solid container prepared in advance in a small container into water and stirring. it can.

The sulfite concentration in the color developer is 1 × 10 ^-2.
It is preferably not more than mol / liter. Especially including 0 7 × 10 ^-3
It is favorable when the amount is less than mol / liter, and particularly preferably 5 × 10 ⁻³ mol / liter or less including 0.

In the present invention, the color developing solution is used at an arbitrary p
Can be used in the H range, but from the viewpoint of rapid processing, pH 9.5 to 13.0
Is preferably used, and more preferably used in the range of 9.8 to 12.0.

The processing temperature for color development is preferably 25 to 70 ° C. The higher the temperature, the shorter the treatment is possible, which is preferable, but it is preferable that the temperature is not too high from the stability of the treatment liquid.
Treatment at 25 to 50 ° C is preferred. Color development time is
It must be 70-240 seconds. If it is shorter than 70 seconds, the maximum density during continuous processing becomes unstable, and if it is longer than 240 seconds, sludge is likely to be generated in the color developing solution. It is preferably in the range of 90 to 220 seconds.

The replenishing amount of the color developing solution is preferably 700 cc or less, more preferably 500 cc or less, per 1 m ² of the light-sensitive material.
More preferably, it is 20 to 280 cc.

The processing steps are essentially composed of a color development step, a bleach-fixing step, and a water washing step (including a stabilizing treatment as an alternative to water washing), but the steps may be added or have the same meaning as long as the finishing effect is not impaired. It can be replaced with a process. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or a bleaching step can be placed before the bleach-fixing step. As the processing step of the color light-sensitive material of the present invention, it is preferable to provide a bleach-fixing step immediately after the color development step.

The bleaching agent that can be used in the bleach-fixing solution is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating a polycarboxylic acid, an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these compounds include compounds 2 to 20 described in JP-A 1-205162, page 18, lower left column to lower right column.

These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution.

As the bleach-fixing solution, a solution containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution comprising a composition containing a large amount of a halide such as ammonium bromide in addition to an ethylenediaminetetraacetic acid iron (III) salt bleaching agent and a silver halide fixing agent, and further ethylenediaminetetraacetic acid iron (III) A special bleach-fix solution having a composition comprising a combination of a salt bleach and a large amount of a halide such as ammonium bromide can be used.

As the above-mentioned halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide or the like may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in a usual fixing process to form a water-soluble complex salt, for example, potassium thiosulfate or thiosulfate. Typical examples are sodium, thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g or more per liter of the bleach-fixing solution, which can be dissolved, but generally 70 to 250 g. The bleach-fix solution contains various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. Alone or 2
It may be contained in combination of two or more species. Further, various optical brighteners, antifoaming agents or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, organic solvents such as methanol, dimethylformamide and dimethylsulfoxide. And the like can be appropriately contained.

The bleach-fixing solution is described in JP-A-46-280,
45-8506, 46-556, Belgian Patents 770,910, Japanese Patent Publications 45-8836, 53-9854, JP-A-54-71634 and 49.
Various bleaching accelerators described in JP-A-42349 and the like can be added.

The pH of the bleach-fixing solution is used at 4.0 or more, but it is generally used in the range of 4.0 to 9.5, preferably 4.
Used in 5-8.5. Most preferably, it is used in the range of pH 5.0 to 8.5. Treatment temperature is below 80 ℃, preferably 55 ℃
It is used after suppressing evaporation etc. The processing time for bleach-fixing is preferably 240 seconds or less.

In the development processing according to the present invention, color development and bleach-fixing are followed by water washing treatment. A preferred embodiment of the water washing treatment will be described below.

Examples of compounds preferably used in the washing solution include chelating agents having a chelate stabilization constant of 8 or more for iron ions. Here, the chelate stabilization constant is the value of Stability Constan by LG Sillen & A.E. Martell.
ts of Metalion Complexes '', The Chemical Society, Lo
ndon (1964) and S. Chaberek & A.E. Martell, "Organic Se
questering Agents ”, Wiley (1959) and others. Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. In addition, the said iron ion means a ferric ion. Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more are described in JP-A 1-205162, page 63, lower right column, line 15 to page 20, upper left column, line 17 Compounds of

The amount of the above chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing solution. Further, an ammonium compound is particularly preferable as the compound added to the washing solution. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof include compounds described in JP-A 1-205162, page 20, upper right column, line 5 to page 20, lower left column, line 11.

The addition amount of the ammonium compound was 1
It is preferably 1.0 × 10 ^-5 mol or more per liter, more preferably in the range of 0.001 to 5.0 mol, particularly preferably
It is in the range of 0.002 to 1.0 mol.

Further, it is desirable that the washing solution contains sulfite within a range where bacteria are not generated. The sulfite contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite and bisulfite. Ammonium sulfate, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite,
Ammonium metabisulfite and hydrosulfite,
Examples thereof include glutaraldehyde bis sodium bisulfite and succinic acid aldehyde bis sodium bisulfite.

It is preferable that at least 1.0 × 10 ^-5 mol of sulfite is added to 1 liter of the washing solution, and 5 × 10 5
^{-5 to} 1.0 × 10 ^-1 mol is more preferable. The method of addition may be such that it is added directly to the washing solution, but it is preferably added to the washing replenisher.

The washing solution used in the present invention preferably contains a mildew-proofing agent, which prevents sulfurization,
It is possible to improve image storability. Examples of such antifungal agents include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds. , Isoxazole-based compounds, propanolamine-based compounds, sulfamide-based compounds, pyronone-based compounds and amino-based compounds. Specific compounds include:
The compounds described in JP-A 1-205162, page 21, upper left column, line 10 to page 22, upper left column, line 16 can be mentioned. Among these compounds, particularly preferably used compounds are thiazole compounds,
They are sulfamide compounds and pyronone compounds.

The addition amount of the antifungal agent to the washing liquid is preferably in the range of 0.001 to 30 g, and more preferably 0.003 to 5 g, per liter of the washing liquid. The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. As such a metal compound, Ba,
Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Z
Examples thereof include compounds of r, Mg, Al and Sr. These metal compounds can be supplied as inorganic or organic salts such as halides, sulfates, carbonates, phosphates and acetates, hydroxides or water-soluble chelate compounds.

The addition amount of these compounds is preferably 1.0 × 10 ^{-4 to} 1.0 × 10 ^-1 mol, and more preferably 4.0 × 10 ^{-4 to} 2.0 × 10 ^-2 mol, per liter of the washing solution.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution. Specific compounds include Exemplified Compounds 1 to 32 described in JP-A 1-205162, page 22, upper right column to lower right column.

The compound having an aldehyde group is preferably used in the range of 0.1 to 50 g, and particularly preferably 0.5 to 10 g, per liter of the washing solution. Further, as the washing water according to the present invention, ion-exchanged water treated with an ion-exchange resin may be used.

The washing water applicable to the present invention has a pH of 5.5 to 1
It is in the range of 0.0. As the applicable pH adjuster, any of commonly known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably 15 to 60 ° C, more preferably 20 to 45 ° C. The washing time is preferably 240 seconds or less. When the washing treatment is carried out in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. In particular, it is preferable to sequentially perform the treatment with the treatment time increased by 20 to 50% in the previous tank.

In the case of the multi-tank counter flow current system, the method of supplying the washing liquid in the washing treatment step is preferably such that the washing liquid is supplied to the post-bath and allowed to overflow into the pre-bath. Of course,
It can also be processed in a single tank. As a method of adding the compound, various methods such as adding as a concentrated solution to the washing tank, or adding the above compound and other additives to the washing solution supplied to the washing tank, and using this as a washing replenisher Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, especially 0.5 to 30 times, the carry-in amount of the pre-bath (normal bleach-fixing solution or fixing solution) per unit area of the light-sensitive material.
Double is preferred. The washing tank in the washing treatment is preferably 1 to 5 tanks, and more preferably 1 to 3 tanks.

As a developing device for the photosensitive material, any known type device may be used. Specifically, it may be a roller transport type in which a photosensitive material is sandwiched between rollers arranged in a processing tank and conveyed, or an endless belt method in which a photosensitive material is fixed to a belt and conveyed, A method of forming a tank in a slit shape, supplying a processing solution to the processing tank and conveying a photosensitive material,
It is also possible to use a spray method in which the treatment liquid is atomized, a web method in which the treatment liquid is brought into contact with a carrier impregnated with the treatment liquid, a method using a viscous treatment liquid, and the like.

In the present invention, a large amount of the light-sensitive material is processed and run in these color development-drying steps to elute components from the light-sensitive material into the processing solution, contamination between processing tanks and evaporation of the processing solution are saturated, The effect is particularly exerted when the treatment is carried out after being stabilized.

[0182]

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

Example 1 Each layer of the following constitution was coated on a 130 μm-thick support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer. Then
A multilayer color light-sensitive material was prepared.

First Layer Coating Liquid Yellow coupler (Y-1) 26.7 g, stain inhibitor (HQ-1) 0.67 g and high boiling point organic solvent (HBS-1)
60cc of ethyl acetate was added to 6.67g to dissolve, and this solution was 20%
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 cc of 10% gelatin aqueous solution containing 7 cc of surfactant (SU-1) using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardener, the second and fourth layers (H
-1) and (H-2) were added to the 7th layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

Layer composition Addition amount (g / m ² ) 7th layer Gelatin 1.00 (Protective film) Anti-stain agent (HQ-1) 0.002 Anti-stain agent (HQ-2) 0.002 Anti-stain agent (HQ-3) 0.004 Anti-staining agent (HQ-4) 0.02 Compounds B, C, D and E 2 × 10 ^-5 DIDP 0.005 Silicon dioxide 0.003 Antifungal agent (F-1) 0.002 6th layer Gelatin 1.50 (UV AI-2 0.04 absorbing layer) ) AI-4 0.02 UV absorber (UV-1) 0.38 UV absorber (UV-2) 0.32 UV absorber (UV-3) 0.54 Stain inhibitor (HQ-4) 0.04 Compound E 4 × 10 ^-4 DNP 0.20 Compounds F and G 2 × 10 ⁻⁴ PVP 0.03 Fifth layer Gelatin 1.3 (Red-sensitive layer) Red-sensitive silver chlorobromide emulsion (Em-R) 0.36 Cyan coupler (C-1) 0.30 Stain inhibitor (HQ-5) ) 0.01 HBS-1 0.20 4th layer Gelatin 1.00 (intermediate layer) Stay Inhibitor (HQ-1) 0.01 Stain preventing agent (HQ-2) 0.01 Stain preventing agent (HQ-3) 0.02 antistain agent (HQ-4) 0.10 Compound B, C, D, E each 2 × 10 ^-5 DIDP 0.03 Antifungal agent (F-1) 0.02 Third layer Gelatin 1.20 (Green-sensitive layer) Green-sensitive silver chlorobromide emulsion (Em-G) 0.30 Magenta coupler (M-1) 0.40 Dye image stabilizer 0.20 HBS-1 0.40 Second layer Gelatin 1.00 (Intermediate layer) AI-1 0.20 AI-3 0.20 Anti-stain agent (HQ-1) 0.03 Anti-stain agent (HQ-2) 0.03 Anti-stain agent (HQ-3) 0.05 Anti-stain agent (HQ) -4) 0.23 Compounds B, C, D and E 3 × 10 ^-4 DIDP 0.06 Optical brightener (W-1) 0.10 First layer Gelatin 1.20 (blue sensitive layer) Blue sensitive silver chlorobromide emulsion (Em- B) 0.28 Yellow coupler (Y-40) 0.80 Anti-stain agent (HQ-4) 0.02 Object ^{A 2 × 10 -4 HBS-1} 0.50 Support Polyethylene laminated paper halide emulsion amount (colorant-containing trace amounts) showed in terms of silver.

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Sulfosuccinate (2,2,3,3,4, 4,5,5-octafluoropentyl) sodium salt DNP: dinonyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro -6-hydroxy-S-triazine sodium

[0188]

[Chemical 17]

[0189]

Embedded image

[0190]

[Chemical 19]

[0191]

Embedded image

[0192]

[Chemical 21]

(Preparation of blue-sensitive silver halide emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
Liquid 3) and (B liquid) are controlled to pH = 7.3 and pH = 3.0.
Simultaneously added over 0 minutes, and further the following (solution C) and (solution D)
Was simultaneously added over 180 minutes while controlling pH = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for the above EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
A monodisperse cubic emulsion EMP with an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1, except that the addition time of (C liquid) and the addition time of (C liquid) and (D liquid) are changed.
-3 was obtained.

The following compounds were used for EMP-3.
Optimal chemical sensitization was carried out at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX Supersensitizer RSS-1 3 × 10 ⁻³ mol / mol AgX The sample thus obtained is referred to as Sample 101 (for comparison).

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0202]

[Chemical formula 22]

Samples 102 to 121 were prepared in the same manner except that the sample 101 was changed as shown in Table 1 and added.

Each sample was exposed to a magenta halftone original film by using a Ratten filter No. 61 manufactured by EK Co., Ltd. as a fluorescent lamp light source and processed according to the following development processing steps. For the exposure, adjust the exposure amount so that the dot gain of the standard printed matter (20% for 50% halftone original) will be adjusted, and the dot gain will be +3.
We also created a sample that would be%. Further, it was subjected to wedge exposure decomposition exposure and processed according to the following development processing steps.

Processing step Processing temperature Time Replenishment amount Color development 37.0 ± 0.3 ℃ 120 seconds 300cc Bleach-fix 35.0 ± 0.5 ℃ 45 seconds 300cc Stabilization 30-35 ℃ 90 seconds 600cc Dry 50-80 ℃ 40 seconds Composition of development processing solution Shown below.

Color developing tank solution and replenishing solution tank solution replenishing solution pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.2g 0.2g potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-hydroxyethyl) -4-aminoaniline sulfate 3.0g 4.0g N, N-diethylhydroxyamine 6.8g 6.0g triethanolamine 10.0g 10.0g sodium diethylenetriamine pentaacetate 2.0g 2.0g 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 liquid had pH = 10.1.
At 0, the replenisher is adjusted to pH = 10.42.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Water was added to bring the total volume to 1 liter, and the pH was adjusted to 6.5 with potassium carbonate or glacial acetic acid.

Stabilizer tank solution and replenisher 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 (Tinopol SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g Ethylenediaminetetraacetic acid / sodium 1.5g Potassium sulfite 5.0g Add water to make 1 liter and add sulfuric acid or ammonia water to adjust pH Adjust to = 8.0. The reflection density of the wedge-exposed and processed sample was measured using a PD-84 densitometer (manufactured by Konica Corporation). X-rite is used to determine the solid density of halftone dot-exposed samples.
It was measured with a 408 densitometer (manufactured by X-rite), and the color tone was measured and evaluated by a CR121 color difference meter (manufactured by Minolta). The color difference from the standard color sample of the printed matter was evaluated.

The dot gain was calculated by using the Murray Davis equation.

DG ₅₀ = [1-10 ^(Db-Dt) ] / [1-10
^(Db-D50) ] × 100-50 DG ₅₀ : Dot gain at 50% Db: White background density D50: 50% halftone dot density Dt: Solid density

[0211]

[Table 1]

The solid density and the color tone of 25% and 50% halftone dot areas were compared with those of a standard print color sample.

As shown in Table 1, the light-sensitive material of the present invention has no discomfort in the color tone in the solid density portion and the halftone dot portion, and the measured value is close to that of the printed matter. Example 2 A sample in which a yellow color-developing green photosensitive layer was provided between the second layer and the third layer of the sample 101 of Example 1 in the following constitution was prepared.

Intermediate layer Gelatin 0.40 (Green-sensitive layer) Green-sensitive silver chlorobromide emulsion (Em-G) 0.060 Yellow coupler 0.07 HBS-1 0.07 Y-32, Y-20, Y-31, Y-as yellow coupler
Samples using 25, Y-41, Y-40, and Y-42 were prepared and evaluated, and as a result, similar effects were obtained.

[0215]

According to the present invention, a high silver chloride emulsion is used when a color proof is prepared from halftone image information obtained by color separation and halftone image conversion using a silver halide color photographic light-sensitive material. Even though the color tone of magenta is not deteriorated, a silver halide color photographic light-sensitive material and a color image forming method can be provided.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having a photosensitive constituent layer containing at least one silver halide emulsion on a support, wherein at least one silver halide emulsion-containing layer has a silver chloride content of 80 mol. % Of blue light density to green light density (DB / DG) in the case of containing a silver halide emulsion having a density of not less than 100% and subjected to green color separation exposure, the low density part (DG = 0.5) and the high density part (DG = 1.5). ) 0.3 to 0.6
A silver halide color photographic light-sensitive material, characterized in that: 2. A silver halide photographic light-sensitive material having a photosensitive constituent layer containing at least one silver halide emulsion on a support, wherein at least one silver halide emulsion-containing layer has a silver chloride content of 80 mol. % Silver halide emulsion, and a magenta coupler and a yellow coupler in the green light-sensitive emulsion layer, which is a silver halide color photographic light-sensitive material. 3. A pKa (pKaM) of a magenta coupler and a pKa (pKaY) of a yellow coupler contained in a green light-sensitive emulsion layer.
3. The silver halide color photographic light-sensitive material according to claim 2, wherein is represented by the following relational expression. 0.1≤ (pKaM-pKaY) ≤2.5 4. A silver halide photographic light-sensitive material having a photosensitive constituent layer containing at least one silver halide emulsion on a support, wherein at least one silver halide emulsion-containing layer has a silver chloride content of 80 mol. % Silver halide emulsion, and a green light-sensitive emulsion containing a yellow light-sensitive emulsion layer containing a yellow coupler and a green light-sensitive emulsion. 5. A silver halide photographic light-sensitive material having a photosensitive constituent layer containing at least one silver halide emulsion on a support, wherein at least one silver halide emulsion-containing layer has a silver chloride content of 80 mol. %, Containing a silver halide emulsion of at least 50% and having a blue light-sensitive emulsion layer containing a yellow coupler and a green light-sensitive emulsion layer containing a yellow coupler in addition to a green light-sensitive emulsion layer containing a magenta coupler. Silver halide color photographic light-sensitive material. 6. A method for producing a color proof by exposing a silver halide light-sensitive material to light on the basis of halftone dot image information consisting of color-separated yellow image information, magenta image information, cyan image information and black image information. The silver halide color light-sensitive material according to any one of claims 1 to 5.
A method for forming a color proof, which comprises exposing the silver halide color photographic light-sensitive material of item 1 to produce a color proof.