JP2002006429A - Silver halide photosensitive material and area gradation image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material which suppresses the deterioration of the quality of dots caused when an area gradation image is formed by development while carrying out replenishment according to the amount of a silver halide photosensitive material processed after scanning exposure in a smaller exposure unit than dots and to provide an image forming method. SOLUTION: In the silver halide photosensitive material with three or more layers each containing silver halide emulsions having sensitivities in different wavelength ranges, the silver halide emulsions are negative type silver halide emulsions having >=95 mol% silver chloride content and grains having the substantially same shape, composition and grain diameter occupy >=80% of all grains in the silver halide emulsions contained in each of the layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photosensitive material capable of forming a stable and excellent area gradation image even in continuous processing, and to an area gradation image forming method using the same. In particular, the present invention relates to a silver halide light-sensitive material capable of forming an area gradation image with less deterioration of dot quality of halftone dots even by continuous processing, and an area gradation image forming method using the same.

[0002]

2. Description of the Related Art Silver halide light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials and light-sensitive materials) are actively used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Used. Due to these characteristics, silver halide light-sensitive materials have been widely used not only in the field of photography but also in the field of printing, in the field of so-called proofing for checking the state of the finished printed matter in the middle of printing. ing.

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

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

For this purpose, various methods such as a fusion heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method of obtaining a high-quality image is expensive and lowers productivity. There is a disadvantage that the system which is low in cost and has high productivity has poor image quality. In a system using a silver halide photosensitive material, it is possible to form an accurate halftone dot image, but on the other hand, it is possible to perform continuous processing as described above, and it is also possible to simultaneously image a plurality of color image forming units. , It was possible to achieve high productivity.

The high productivity of a system using a silver halide light-sensitive material has been particularly useful when trying to obtain a plurality of identical images. However, the silver halide photosensitive material is scanned and exposed with a semiconductor laser (LD) or light emitting diode (LED) in a unit smaller than a halftone dot, and developed while replenishing a developing solution according to the amount of the processed silver halide photosensitive material. It has been found that as the processing is performed, the end portions of the halftone dots are blurred, and the portions that should originally be uniformly colored have portions in which the density varies in a granular manner.

JP-A-62-153857 discloses a silver halide light-sensitive material having a blue, green, and red light-sensitive silver halide emulsion layer on a support.
The ratio of the maximum average particle size to the minimum average particle size is 1.3 or less, the average particle size of the emulsion in each emulsion layer is 0.6 μm or less, and the blue-sensitive silver halide emulsion has a specific spectral A silver halide photosensitive material containing a sensitizing dye and a specific yellow coupler enables rapid processing, high sensitivity, low fog, little residual color contamination of the sensitizing dye, etc. Are disclosed.

However, after scanning and exposing with an exposure unit smaller than the halftone dot, and developing while performing replenishment in accordance with the amount of the processed silver halide photographic material, the halftone dot generated when an area gradation image is formed is formed. There is no suggestion of improving the deterioration of the poison.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a scanning exposure unit having an exposure unit smaller than a halftone dot.
Silver halide light-sensitive material and area gradation image forming method with improved halftone dot quality deterioration that occurs during formation of an area gradation image by developing while performing replenishment in accordance with the amount of the processed silver halide light-sensitive material Is to provide.

[0010]

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

1. In a silver halide light-sensitive material having three or more layers each containing a silver halide emulsion having sensitivity to a different wavelength region, the silver halide emulsion is a negative-working silver halide emulsion comprising 95 mol% or more of silver chloride. And the silver halide grains in the silver halide emulsion contained in each layer are substantially the same in shape, composition, and grain size as 80% of all silver halide grains.
A silver halide photosensitive material characterized by the above.

2. In a silver halide light-sensitive material having three or more layers each containing a silver halide emulsion having sensitivity to a different wavelength region, the silver halide emulsion is a negative-working silver halide emulsion comprising 95 mol% or more of silver chloride. And the silver halide grains in the silver halide emulsion contained in each layer are substantially the same in shape, composition, and grain size as 80% of all silver halide grains.
The silver halide light-sensitive material as described above, wherein the average particle diameter of the silver halide grains in each layer is 0.56 μm or less.

3. 3. The halogen according to the above item 1 or 2, wherein the silver halide emulsion of each layer contains at least one compound selected from the compounds represented by the general formula (SP-I) or (SP-II). Silver halide photosensitive material 4. The silver halide light-sensitive material according to the item 3, wherein the compound represented by the general formula (SP-II) is the general formula (SP-III) or (SP-IV).

5. In a silver halide photographic material having three or more layers each containing a silver halide emulsion having sensitivity to a different wavelength region, the silver halide emulsion is a negative-working silver halide emulsion comprising 95 mol% or more of silver chloride. And the silver halide grains in the silver halide emulsion contained in each layer having substantially the same shape, composition, and particle size as silver halide grains account for 80% of all silver halide grains.
A silver halide light-sensitive material characterized in that the silver halide light-sensitive material further comprises a compound represented by the formula (I) or (II) in one of the layers.

6. Area gradation image formation in which a silver halide photosensitive material having a silver halide emulsion layer on a support is scanned and exposed in exposure units smaller than halftone dots, and then developed while replenishing according to the amount of the silver halide photosensitive material. An area gradation image forming method, wherein the silver halide photosensitive material is the silver halide photosensitive material according to any one of the above items 1 to 5.

Hereinafter, the present invention will be described in more detail. One of the features of the present invention is that in a silver halide light-sensitive material having three or more layers each containing a silver halide emulsion having sensitivity to a different wavelength region, the silver halide emulsion has a sensitivity of 9 or more.
At least 5 mol% is a negative silver halide emulsion comprising silver chloride, and each of the silver halide grains in the silver halide emulsion contained in each layer has substantially the same shape, composition and grain size. The same silver halide grains are at least 80% of all silver halide grains.

The negative type silver halide emulsion referred to herein is
It means a type in which the amount of silver halide developed increases as the amount of exposed light increases. In such an emulsion type, a phenomenon that the amount of developed silver halide is reduced by exposure to an excessive amount of light is also observed, but it can be determined by the exposure amount in the range used for image formation. Good.

The phrase "substantially the same shape" means that the ratio of crystal planes on the surface of silver halide grains does not differ by 10% or more, but is preferably 5% or less, more preferably 3% or less. The ratio of the crystal planes on the surface of the silver halide grains can be determined by using a known method such as a method based on X-ray diffraction or a method obtained from the adsorption amount of a specific sensitizing dye having surface selectivity for adsorption. is there.

The fact that the compositions are substantially the same means that the difference in halide ion content does not differ by 5% or more, but is preferably 3% or less, more preferably 2% or less.

The phrase "substantially no difference in particle size" means that the average particle size does not differ by 10% or more, but preferably 5% or less, more preferably 3% or less.

A feature of the present invention resides in a silver halide emulsion containing 95 mol% or more of silver chloride. As long as 95 mol% or more of silver halide emulsion is composed of silver chloride, it may have any halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide. A silver chlorobromide containing 95 mol% or more of silver, particularly a silver halide emulsion having a portion containing silver bromide at a high concentration, is preferably used. Silver chloroiodide containing 5 mol% is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy region in which only a region having a partially different composition may exist may be formed. It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or discontinuously.

The negative working silver halide emulsion comprising 95% or more of silver chloride of the present invention advantageously contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and softening on the shadow side.

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

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

In order for the heavy metal ion to be contained in the silver halide emulsion, the heavy metal compound is subjected to various steps during physical ripening before formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. May be added at any location.

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

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

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

The silver halide grains of the present invention may have any shape. One preferred example is (1
It is a cube having the (00) plane as the crystal surface.

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

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

The grain size of the silver halide grains of the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. It is in the range of 0.2 to 1.0 μm, particularly preferably 0.2 to 0.56 μm.

The grain size can be measured by using the projected area of the silver halide grain or an approximate value of the diameter. If the silver halide grains are substantially uniform in shape, the grain size distribution can represent this quite accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient of 0 or less. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The apparatus and method for preparing a silver halide emulsion (hereinafter also simply referred to as an emulsion) include: Various methods known in the art can be used.

The emulsion of the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The emulsion may be grown at a time or may be grown after seed grains have been formed. The method of producing the seed particles and the method of growing them may be the same or different.

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

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

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

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

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

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 1 per mol of silver halide.
It is preferably from 0 ^-4 mol to 1 × 10 ^-8 mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization method of the negative silver halide emulsion comprising 95% or more of silver chloride used in the present invention includes:
A reduction sensitization method may be used.

The silver halide emulsion of the present invention is known for the purpose of preventing fog generated during the preparation of a silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Antifoggants and stabilizers can be used.

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

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

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

In the light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-251840.
The dyes of AI-1 to 11 described on page 308 and dyes described in JP-A-6-3770 are preferably used.

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

The silver halide light-sensitive material of the present invention comprises a halogenated light-sensitive material.
Silver halide emulsion closest to the support in the silver halide emulsion layer
At least one layer of colored parent closer to the support than the layer
It is preferable that the hydrophilic colloid layer has an aqueous colloid layer.
The id layer may contain a white pigment. For example rutile
Type titanium dioxide, anatase type titanium dioxide, sulfuric acid burr
, Barium stearate, silica, alumina, oxide
Zirconium, kaolin, etc. can be used,
For various reasons, titanium dioxide is particularly preferred. White face
The material is hydrophilic, such as gelatin, so that the processing solution can penetrate.
The aqueous colloid is dispersed in an aqueous binder. White face
The amount of the coating applied is preferably 0.1 g / m ^Two~ 50g / m^Two
And more preferably 0.2 g / m^Two~ 5g /
m^TwoRange.

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

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

The silver halide light-sensitive material of the present invention contains 40
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength range of 0 to 900 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

One feature of the silver halide light-sensitive material of the present invention is that it contains at least one sensitizing dye selected from the sensitizing dyes represented by formula (SP-I) or (SP-II). It is to be.

In the general formula (SP-I), Z ₁₁ and Z ₁₂
Are oxazole nucleus, thiazole nucleus, selenazole nucleus, pyridine nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, naphthooxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, naphthoimidazole nucleus or quinoline Represents the group of atoms required to form a nucleus. R ₁₁ and R ₁₂ each represent an alkyl group, an alkenyl group or an aryl group. X ⁻ represents an anion, and m represents 0 or 1. However, when an inner salt is formed, m represents 0.

As the heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ , a benzothiazole nucleus, a benzoselenazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus and a naphthoxazole nucleus are preferable.

The heterocyclic group represented by Z ₁₁ and Z ₁₂ may have a substituent. Preferred substituents include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group, and a heterocyclic group. And a ring group.

Among the halogen atoms, a particularly preferred one is a chlorine atom, and the aryl group is preferably a phenyl group.

The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, i-propyl and butyl. .

The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and includes groups such as methoxy, ethoxy and propoxy. Of these, a methoxy group is preferable.

Examples of the heterocyclic group include a heterocyclic group derived from a pyrrole ring, a pyridine ring, a thiophene ring, a furan ring and the like.

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

Specifically, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, carboxymethyl, 2-carboxyethyl, 2-ethoxycarbonylethyl, 2-hydroxyethyl, 2-methylsulfonylaminoethyl and the like Of each group.

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

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

[0067] X ^- include anions represented by the chloride, bromide, and iodide ion or p- toluenesulfonate ion and the like are preferable, halide ions are preferred.

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

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

[0070]

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[0071]

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[0072]

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[0073]

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In the general formula (SP-II), Z ₂₁ and Z ₂₂
Are oxazole nucleus, thiazole nucleus, selenazole nucleus, pyridine nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, naphthooxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, naphthoimidazole nucleus or quinoline Represents the group of atoms required to form a nucleus.

R ₂₁ and R ₂₂ are the same as R ₁₁ and R _{12 in} formula (SP-I), respectively, and X ⁻ and m are the same as in formula (SP-I).
Represents the same as I).

R ₂₃ represents a hydrogen atom, an alkyl group or an aryl group. The heterocyclic groups represented by Z ₂₁ and Z ₂₂ may have a substituent, and preferred substituents are the same as those described for Z ₁₁ and Z ₁₂ in formula (SP-I). Can be mentioned.

The alkyl group represented by R ₂₃ is preferably an ethyl group or a propyl group, and the aryl group is preferably a phenyl group.

Specific examples of the color sensitizer represented by the general formula (SP-II) include the following compounds.

[0079]

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[0080]

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[0081]

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Among the sensitizing dyes represented by formula (SP-II), preferred sensitizing dyes are the compounds represented by formula (SP-III).

In the general formula (SP-III), R ₃₁
And the substituted alkyl group represented by R ₃₃ are, for example, a hydroxyethyl group, an ethoxycarbonylethyl group, an ethoxycarbonylmethyl group, an allyl group, a benzyl group, a phenethyl group, a methoxyethyl group, a methanesulfonylaminoethyl group, Examples of the group include an oxobutyl group and the like, and examples of the unsubstituted alkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group.

The lower alkyl group represented by R ₃₂ and R ₃₄ includes, for example, groups such as a methyl group, an ethyl group, a propyl group, a butyl group and a trifluoroethyl group. Examples of the group include carboxymethyl, carboxyethyl, methanesulfonylaminoethyl, sulfobutyl, sulfoethyl, sulfopropyl, sulfopentyl, 6-sulfo-3-
Oxahexyl group, 4-sulfo-3-oxapentyl group, 10-sulfo-3,6-dioxadecyl group, 6-sulfo-3-thiahexyl group, o-sulfobenzyl group, p
-Carboxybenzyl group and the like.

The substituent represented by each of V ₁ , V ₂ , V ₃ and V ₄ may be any group as long as the sum of Hammett σp values of the substituents does not exceed 1.7. All right,
For example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (methyl group, ethyl group, t
-Butyl group), an alkoxy group (such as a methoxy group), an alkylthio group (such as a methylthio group), a trifluoromethyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group (such as a methoxycarbonyl group and an ethoxycarbonyl group), and an acyl group ( Acetyl group), sulfonyl group (methanesulfonyl group), carbamoyl group (carbamoyl group,
N, N-dimethylcarbamoyl group, N-morpholinocarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N, N-dimethylsulfamoyl group, etc.), acetylamino group, acetyloxy group and the like.

The ion necessary for neutralizing the charge in the molecule represented by X ^- may be either an anion or a cation. Examples of the anion include a halide ion (chloride ion, bromide ion, iodine ion). Chloride ion, perchlorate ion, ethyl sulfate ion, thiocyanate ion, p-toluenesulfonic acid ion, perfluoroborate ion and the like. Examples of the cation include hydrogen ion, alkali metal ion (lithium ion, sodium ion) , Potassium ions, etc.),
Examples include alkaline earth metal ions (magnesium ions, calcium ions, etc.), ammonium ions, organic ammonium ions (triethylammonium ions, triethanolammonium ions, tetramethylammonium ions, etc.).

Preferable substituents represented by V ₁ , V ₂ , V ₃ and V ₄ are groups which give S values derived from S = 2L / (B1 + B2 + B3 + B4) smaller than 1.0. Here, L, B1, B2, B3 and B4 are STERI.
Represents the MOL parameter.

Specifically, a methyl group (S = 0.81)
5), an ethyl group (S = 0.992), a t-butyl group (S
= 0.728), a methoxy group (S = 0.993), a methylthio group (S = 0.982), a trifluoromethyl group (S = 0.697), an acetyl group (S = 0.893),
Methanesulfonyl group (S = 0.825), carboxyl group (S = 0.877), carbamoyl group (S = 0.9
3), a group such as a sulfamoyl group (S = 0.726), a fluorine atom (S = 0.981), a chlorine atom (S = 0.97)
8) and a bromine atom (S = 0.982).

The Hammett σp value used in the general formula (SP-III) is a substituent constant determined from the electronic effect of the substituent on the hydrolysis of the benzoate by Hammett et al., And the STERIMOL parameter is It is a value defined by a length obtained from a projection view with respect to a bonding axis with a benzene nucleus, and is described in Journal of Organic Chemistry, Vol. 23, 420-427 (1958),
Edited by The Chemical Society of Japan, Experimental Chemistry Lecture Vol. Nanedo: 1979).

Next, specific representative examples of the photosensitive dye represented by formula (SP-III) preferably used in the present invention are shown below.

[0091]

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[0092]

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[0093]

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[0094]

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The above compounds are generally known, and can be easily synthesized, for example, by the method described in Hammer, "The Cyanine Soybean and Related Compounds" (Interscience Publishers, New York, 1969). be able to.

Among the compounds represented by the above formula (SP-II), preferred compounds are those represented by the above formula (SP-IV).

In formula (SP-IV), Z ₄₁ and Z ₄₂ each represent an atomic group necessary for forming a benzothiazole nucleus and a naphthothiazole nucleus.

R ₄₁ and R ₄₂ are the same as R ₁₁ and R _{12 in} formula (SP-I), respectively, and X ⁻ and m are the same as those in formula (SP-I).
Represents the same as I).

R ₄₃ represents a hydrogen atom, an alkyl group or an aryl group. The compounds are generally known, and can be easily synthesized, for example, by the method described in Harmer, "The Cyanine Soybean and Related Compounds" (Interscience Publishers, New York, 1969). .

As the spectral sensitizing dye used in the silver halide emulsion of the present invention, known compounds can be used, and as the blue-sensitive sensitizing dye, JP-A-3-25184.
No. 0, page 28, BS-1 to BS-8 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include GS-1 to GS-5 described on page 28 of the same publication.
Is preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes.

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

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

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

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

In using these dispersing apparatuses, a method may be employed in which pretreatment such as dry pulverization is performed in advance and then wet dispersing is performed as described in JP-A-4-125632.

The silver halide emulsion of the present invention may be one kind or
Two or more sensitizing dyes may be contained in combination.

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

As the magenta coupler used in the light-sensitive material of the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of excellent spectral absorption characteristics of a coloring dye. Specific examples of preferred compounds include Compound M- described on pages 8 to 11 of the same publication.
1 to M-19. Still other specific examples include compounds M-1 to M-61 and 235,913 described in EP 273,712, pp. 6-21.
Among the compounds 1-223 described on pages 36-92, there are other than the representative examples described above.

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

The λmax of the spectral absorption of the magenta image formed in the light-sensitive material of the present invention is preferably 530-560 nm, and λL0.2 is 580-63.
Preferably it is 5 nm. λL0.2 means that the maximum absorbance is 1. on the spectral absorbance curve of the magenta image.
A wavelength longer than the wavelength indicating 0 and having an absorbance of 0.2.

The magenta image forming layer of the silver halide light-sensitive material of the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5.

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

Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283 and JP-A-2-13954.
No. 2, pages 13 to 17 (Y-
1) to (Y-58) can be preferably used, but are not limited thereto.

As the cyan coupler contained in the cyan image forming layer in the light-sensitive material of the present invention, known phenol, naphthol, imidazole or azole couplers can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a 2-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are represented. You. Among them, preferred compounds are described in JP-A-6-9 / 1994.
General formula [C-I] [C-I] described on page 13 of No. 5283
I].

The azole cyan coupler of the invention according to claim 5 of the present invention is a cyan coupler represented by the above general formulas (I) and (II).

In the general formula [I], when m1 is 0, R
₁ represents an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more. When m1 is 1 or 2 or more, at least one of R ₁ and R ₂ has a Hammett's substituent constant σ _P of 0 or more. Represents 20 or more electron-withdrawing groups.

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

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

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

In the general formula [I], among the substituents represented by R ₁ and R ₂ , examples of the substituent other than the electron-withdrawing group include, but are not particularly limited to, typical ones. , Alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl,
Heterocycle, alkoxy, aryloxy, heterocycleoxy,
Siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, and spiro compound residues And bridged hydrocarbon compound residues.

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

As the acylamino group, an alkylcarbonylamino group or an arylcarbonylamino group; as the sulfonamide group, an alkylsulfonylamino group or an arylsulfonylamino group; Groups.

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

As the ureido group, an alkylureido group,
An arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a 5- to 7-membered heterocyclic group is preferable, specifically a 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- A phenyltetrazol-5-oxy group or the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, or a 2,4-diphenoxy-1,3 , 5-
Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group,
3-heptadecyl succinimide group, phthalimide group, glutarimide group and the like; spiro compound residue such as spiro [3.3] heptane-1-yl; bridged hydrocarbon compound residue as bicyclo [2.2. 1] heptan-1-yl, tricyclo [3.3.1.1 ^37] decane-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

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

In the general formula [I], examples of a group or atom capable of leaving by reaction with an oxidized form of the color developing agent represented by X ₁ include a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom and the like). ) And alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy,
Alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom, alkoxycarbonylamino, Examples include groups such as aryloxycarbonylamino and carboxyl. Of these, preferred are a hydrogen atom and a nitrogen-containing heterocyclic group bonded with an alkoxy, aryloxy, alkylthio, arylthio, or N atom.

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

The compounds represented by the general formula [I] are more specifically represented by the following general formulas [I] -1 and [I] -2.

[0129]

Embedded image

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

[0131] X ₁ has the same meaning as X ₁ in the general formula (I). In general formulas [I] -1 and [I] -2,
Among R ₁ , R ¹¹ and R ¹² , those which are not electron-withdrawing groups having σ _P of 0.20 or more represent a hydrogen atom or a substituent.

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

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

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

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

[0136]

Embedded image

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

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

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

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

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

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

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

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

The λL0.2 of the spectral absorption of a yellow image is described in JP-A-6-95283, page 21, right column, lines 1 to 24.
This is a value defined by the content described in the row, and represents the magnitude of unnecessary absorption on the long wave side in the spectral absorption characteristics of the yellow dye image.

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

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

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

An anti-fading agent can be used in combination with each of the magenta, cyan, and yellow couplers to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by the general formulas I and II described on page 3 of JP-A-2-66541, phenol compounds represented by the general formula IIIB described in JP-A-3-174150, and
Amine compounds represented by the general formula A described in JP-A-90445; compounds represented by the general formulas XII and XII described in JP-A-62-182741;
Metal complexes represented by I, XIV and XV are particularly preferred for magenta dyes. Also, a compound represented by formula I 'described in JP-A-1-19649 and JP-A-5-11417.
The compound represented by the general formula II described above is particularly preferable for yellow and cyan dyes.

When the oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide light-sensitive material of the present invention, the boiling point is usually 150 ° C.
The above-mentioned water-insoluble high-boiling organic solvent is dissolved, if necessary, in combination with a low-boiling and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalic acid esters such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. And phosphine oxides such as trioctylphosphine oxide are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

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

A surfactant in which an alkyl group is substituted with a fluorine atom is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

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

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by formula II described in JP-A-1-250944.
A compound represented by the formula (I-3); a compound represented by the formula III described in JP-A-64-66646;
No. 240, UV-1L to UV-27L;
No. 1633, a compound represented by the general formula I
Compounds represented by general formulas (I) and (II) described in JP-A-165144.

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

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, proteins other than gelatin, A hydrophilic colloid such as a derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153.

Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, Japanese Patent Laid-Open Publication No.
It is preferable to add a preservative and an antifungal agent as described in JP-A-157646.

In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

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

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

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

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

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support was 13% by mass for improving sharpness.
The above is preferred, and more preferably 15% by mass.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Although the term "area gradation image" is used in the present invention, this is not to express the shading on the image by the shading of the color of each pixel, but to determine the size of the area of the portion colored to a specific density. And can be considered as synonymous with halftone dots.

In the area gradation image forming method of the present invention, a unit (expressed as a dot) in which pixels are further subdivided is considered, dots are formed by light emitted from various light sources, and the number of halftone dots is determined by the number thereof. For example, a method of changing the length is used.

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

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

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

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

The silver halide light-sensitive material of the present invention, in which the surface on the side to be exposed is wound outward, can be more accurately positioned and can be preferably used. From the same viewpoint, the support used in the silver halide light-sensitive material of the present invention has an appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.

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

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

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

CD-1) N, N-Diethyl-p-phenylenediamine CD-2) 2-Amino-5-diethylaminotoluene CD-3) 2-Amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N-ethyl-N-
(Β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N
-(Γ-hydroxypropyl) aniline In the present invention, the color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0, more preferably pH 9.8. ~ 12.
Used in the range of 0.

The processing temperature for color development used in the present invention is preferably 35 ° C. to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high.

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

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

The silver halide light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

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

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

[0199]

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

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

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

[0202]

[Table 1]

[0203]

[Table 2]

[0204]

Embedded image

[0205]

Embedded image

[0206]

Embedded image

[0207]

Embedded image

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- Mixture of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone at a mass ratio of 1: 1: 2 SO-1: trioctylphosphine oxide SO-4: tricresyl phosphate PVP: polyvinyl Pyrrolidone (Preparation of blue-sensitive silver halide emulsion) 2
(A solution) and (B)
Solution) and pAg = 7.3 at the same time while controlling to pH = 3.0, and the following (Solution C) and (Solution D) were further pAg = 8.
0, pH = 5.5. At this time,
The pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml After desalting was performed using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-101 was obtained.

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

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye (SP-I-3) 4 × 10 ^-4 mol / mol AgX sensitizing dye (SP-I-11) 1 × 10 ^-4 mol / mol AgX (Preparation of Green-Sensitive Silver Halide Emulsion) EMP-101
The average particle size was 0.40 μm, the coefficient of variation was 0.08, and the silver chloride content was the same except that the addition times of (Solution A) and (Solution B), (Solution C) and (Solution D) were changed in the preparation of 9
A 9.5% monodisperse cubic emulsion (EMP-102) was obtained.

The above-mentioned EMP-102 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain a green-sensitive silver halide emulsion (Em-G101).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye SP-II-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) EMP-102
The following compounds were optimally subjected to chemical sensitization at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R101).

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye SP-II-10 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye SP-II-11 1 × 10 ⁻⁴ mol / mol AgX STAB-1 : 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole (A solution) and (B)
Solution), (C solution) and (D solution), except that the addition time was changed, the average particle diameter was 0.60 μm, and the variation coefficient was 0.0.
8. Monodisperse cubic emulsion EMP having a silver chloride content of 99.5%
-103 was obtained.

(Em-B1)
01), (Em-G101) and (Em-R101) using the compounds used in the preparation and adjusting the conditions to carry out optimal chemical sensitization to give (Em-B102), (Em-G102),
(Em-R102) was prepared.

In the preparation of Sample 101, (Em-B10
1), (Em-G101) and (Em-R101) instead of the silver halide emulsions (Em-B102) and (Em-G101)
G102) and (Em-R102) to prepare Sample 102.

Hereinafter, in the same manner as in the preparation of EMP-101, except that the addition time of (Solution A) and (Solution B), (Solution C) and (Solution D) was changed, the average particle diameter was 0.50.
A monodisperse cubic emulsion EMP-104 having a particle size of 0.09 μm, a coefficient of variation of 0.09, and a silver chloride content of 99.5% was prepared, and blue, green and red-sensitive emulsions were prepared and coated using the prepared emulsion.
A blue-sensitive emulsion was prepared using MP-102, and (Em-G
101), sample 10 in combination with (Em-R101)
4 was prepared.

Further, in the preparation of Sample 102, the total amount of the blue-sensitive emulsion was kept constant, and (Em-B101) and (Em-B102) were mixed at a ratio of 15:85 and 30:70 to prepare Samples 105 and 106. Was prepared.

By arranging ten B, G, and R LEDs as light sources in the main scanning direction, the timing of exposure was gradually delayed so that the same location could be exposed by ten LEDs. Also, an exposure head was prepared in which ten LEDs were arranged in the sub-scanning direction, and exposure for ten adjacent pixels could be performed at one time.

The exposure level was adjusted for each sample so that the G density in status T when black was developed was 1.80. As a pattern to be exposed, one halftone dot
A pattern was formed so as to expose 50% of the dots by expressing them as × 10 dots, and a patch image of four colors of black, yellow (Y), magenta (M), and cyan (C) was combined with a portrait image .

Next, a developed film having substantially the same image as that of the image was prepared, and the film was brought into close contact with the samples 101 and 102, and the entire surface was subjected to decomposition exposure to adjust the conditions under which a similar image could be obtained.

Processing step Processing temperature Time Replenishment amount Color development 33.0 ± 0.3 ° C. 120 seconds 80 ml Bleaching and fixing 33.0 ± 0.5 ° C. 90 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60-80 30 ° C. Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β-hydroxyethyl) -4-aminoaniline sulfate 2.9 g 4.8 g N, N-diethylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0g 2.0g Optical brightener (4,4'- The is added to make 1 liter diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g water tank solution to pH = 10.0, replenishing solution is adjusted to p H = 10.6.

Bleach-fix bath solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

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

After outputting the first images for the samples 101 and 102, the images were continuously exposed and developed, and the amount of the replenished developer was 0.75 and 1.5 times the volume of the developer tank. Then, the sample was taken out, and based on the black dot image (sample 101) of the first film contact exposure, the sharpness of the end of the halftone dot and the uniformity of the density of the colored portion were determined as 10%.
Relative comparison by human subjects. Assuming that the reference image is 3,
4 was determined to be superior, and 2 was determined to be degraded.
Even worse products were evaluated on a scale of 1 to 5, and the average value was used as the evaluation value of the sample. The results are shown below.

[0226]

[Table 3]

In the case where the film contact exposure was performed, there was almost no deterioration in the image quality due to the repeated development of the samples 101 and 102, and this problem was a peculiar phenomenon caused by the scanning exposure. I understand. As a result of scanning exposure, it can be seen that deterioration was observed in the sample 101 having a large blue-sensitive emulsion. Samples 102 to 104, in which three photosensitive emulsions were prepared from the same silver halide emulsion, showed that although there were slight variations, the variations were greatly improved. The smaller the average grain size of the silver halide grains, the smaller the variation in dot quality tends to be.
It can be seen that the effect is almost saturated when the particle size is about 0.5 μm.

It is not preferable to mix emulsions having different particle diameters which cannot be regarded as substantially the same, since the effect of the present invention is undesirably reduced. However, the effect can still be recognized with the mixing of about 15%. It was found that almost no effect was observed with 30% mixing.

As a result of enlarging and observing the image of the sample 101, the image is defocused as a whole, the sharpness of the end of the halftone dot is lost, and the unevenness of the color-developed portion tends to increase. It is understood that there is. In the portrait image, the color sharpness was slightly reduced.
In the sample 102, almost no change in the image quality of the portrait image was recognized.

Example 2 In the preparation of EMP-103 of Example 1, chloride was changed in the same manner except that the amounts of the halide salts of (solution A), (solution B), (solution C) and (solution D) were changed. EMP with silver content of 97%
-201 and 94% EMP-202 were prepared.

In the preparation of the blue-sensitive emulsion of Sample 102, E
MP-103 (Em-B102) is converted to EMP-201 (E
m-B201) and EMP-202 (Em-B202).
02 was produced.

Further, in the preparation of Sample 102, the total amount of the blue-sensitive emulsion was kept constant, and (Em-B102) and (Em-B202) were mixed at a ratio of 15:85 and 30:70 to prepare Samples 203 and 204. Was prepared.

The same evaluation as in Example 1 was performed by using this, and the result is shown below.

[0234]

[Table 4]

The silver chloride content of the blue-sensitive emulsion was 94% in Sample 202, which was 5.5% different from other silver halide emulsions. This is a comparative example. It can be seen that the quality tends to deteriorate.
In the sample 201 in which the composition difference is only 2.5%, the sample 102
It is clear that there is no significant difference from the above, and it is stable.

In Samples 203 and 204, emulsions having different compositions were mixed. In Sample 203 in which an emulsion having a silver chloride content of 94% was mixed in 15%, the effect of the present invention could be recognized, but 30% was mixed. In Sample 204, the effect of the present invention was not observed.

Example 3 In preparing the green-sensitive emulsion of Sample 102 of Example 1, the sensitizing dyes were SP-II-1 to SP-III-3 and SP-III-
Samples 301 and 302 were produced in the same manner except that the sample No. 8 was changed. Similarly, in the preparation of the red-sensitive emulsion of Sample 102, Sample 303 was prepared in the same manner except that the combination of SP-II-10 and SP-II-11 was changed to RS-1 and RS-2. .

Using this, the same evaluation as in Example 1 was performed, and the results are shown below.

[0239]

Embedded image

[0240]

[Table 5]

It can be seen that the samples using the silver halide light-sensitive material of the present invention show little change in halftone dot quality and high stability even when the development is continued due to the effect of the present invention. Among them, a sample using a compound represented by the general formula (SP-III) as a sensitizing dye for a green-sensitive emulsion, and a compound represented by the general formula (SP-II) as a sensitizing dye for a red-sensitive emulsion It turns out that the used sample shows an excellent effect.

Example 4 Sample 401 was prepared in the same manner as in Preparation of Sample 102 of Example 1, except that the cyan coupler (C-11) was changed to an equimolar (C-21). )
0.4 g / m ² , 0.35 g of red-sensitive silver halide emulsion
Sample 402 was prepared in the same manner except that the sample 402 was changed to / m ² .

Using this, the same evaluation as in Example 1 was performed, and the results are shown below.

[0244]

Embedded image

[0245]

[Table 6]

It was confirmed that all the samples using the silver halide light-sensitive material of the present invention exhibited the effects of the present invention. In the samples 102 and 401 using the cyan couplers represented by the general formulas [I] and [II], excellent color reproducibility was confirmed even in portrait images, but the effect of the present invention was slight but higher. The effect is obtained, which is preferable.

[0247]

The silver halide light-sensitive material and the image forming method according to the present invention are characterized in that, after scanning exposure with an exposure unit smaller than a halftone dot, development is performed while replenishing according to the amount of the processed silver halide light-sensitive material. And thereby has an excellent effect of improving the deterioration of the dot quality of halftone dots which occurs when an area gradation image is formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/18 G03C 1/18 5/08 5/08 7/00 540 7/00 540 7/38 7 / 38 7/44 7/44

Claims (6)

[Claims] 1. A silver halide light-sensitive material having three or more layers each containing a silver halide emulsion having sensitivity to a different wavelength region, wherein the silver halide emulsion is 95% by mole or more of silver chloride. A silver halide emulsion in which each silver halide grain in the silver halide emulsion contained in each layer has substantially the same shape, composition, and particle size as 80% of all silver halide grains. %
A silver halide photosensitive material characterized by the above. 2. A silver halide light-sensitive material having three or more layers each containing a silver halide emulsion having sensitivity to a different wavelength region, wherein the silver halide emulsion is 95% by mole or more of a negative-working silver halide emulsion. A silver halide emulsion in which each silver halide grain in the silver halide emulsion contained in each layer has substantially the same shape, composition, and particle size as 80% of all silver halide grains. %
The silver halide light-sensitive material as described above, wherein the average particle diameter of the silver halide grains in each layer is 0.56 μm or less. 3. The silver halide emulsion of each layer contains at least one compound selected from compounds represented by the following general formula (SP-I) or (SP-II). Or the silver halide light-sensitive material according to item 2. Embedded image [In the formula, Z ₁₁ and Z ₁₂ each represent an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, a pyridine nucleus, a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, It represents an atomic group necessary for forming a selenazole nucleus, a naphthoimidazole nucleus or a quinoline nucleus. R ₁₁ and R ₁₂ each represent an alkyl group, an alkenyl group or an aryl group. X ⁻ represents an anion, and m represents 0 or 1. However, when an inner salt is formed, m represents 0. [Chemical formula 2] [In the formula, Z ₂₁ and Z ₂₂ each represent an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, a pyridine nucleus, a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, It represents an atomic group necessary for forming a selenazole nucleus, a naphthoimidazole nucleus or a quinoline nucleus. R ₂₁ and R ₂₂ are respectively R ₁₁ and R of the general formula (SP-I)
The same thing as _12, X ^-, m represents the same thing as in the formula (SP-I). R ₂₃ represents a hydrogen atom, an alkyl group or an aryl group. ] 4. The silver halide according to claim 3, wherein the compound represented by the general formula (SP-II) is the following general formula (SP-III) or (SP-IV). Photosensitive material. Embedded image [Wherein, R ₃₁ and R ₃₃ each represent a substituted or unsubstituted alkyl group, at least one of R ₃₁ and R ₃₃ is a group other than an ethyl group, and R ₃₂ and R ₃₄ are lower groups. Represents an alkyl group, and one of R ₃₂ and R ₃₄ is an alkyl group substituted with a hydrophilic group. V ₁ , V ₂ , V ₃ and V ₄ each represent a hydrogen atom or a substitutable group having a sum of Hammett σp values of less than 1.7, and V _{1 to} V ₄ represent a hydrogen atom or a chlorine atom simultaneously Does not. X represents an ion required to neutralize the intramolecular charge, and n represents the number of ions required to cancel the intramolecular charge. [Formula 4] [In the formula, Z ₄₁ and Z ₄₂ each represent an atom group necessary for forming a benzothiazole nucleus and a naphthothiazole nucleus. R
₄₁ and R ₄₂ are the same as R ₁₁ and R ₁₂ in the general formula (SP-I), and X ⁻ and m are the same as those in the general formula (SP-I). R ₄₃ represents a hydrogen atom, an alkyl group or an aryl group. ] 5. A method having sensitivity in different wavelength ranges.
Halogen having three or more layers containing silver halide emulsion
In a silver halide light-sensitive material, the silver halide emulsion is 95 mol
% Or more of silver chloride emulsion comprising silver chloride.
And the halogen in the silver halide emulsion contained in each layer
Substantially the same shape, composition and particle size of silver halide particles
Is 80% of all silver halide grains
And the following general formula is added to any one of the layers.
Contains a compound represented by [I] or the general formula [II]
A silver halide light-sensitive material, characterized in that: Embedded image[Wherein, R₁Represents a hydrogen atom or a substituent;_TwoIs a substituent
Represents m1 is a substituent R _TwoIndicates the number of When m1 is 0,
R₁Is an electron whose Hammett's substituent constant σp is 0.20 or more.
Represents an attractive group, and when m1 is 1 or 2 or more, R₁And R_Two
At least one has a Hammett's substituent constant σp of 0.2
Represents 0 or more electron withdrawing groups. Z₁Is a benzene ring
Necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be combined
Represents a non-metallic atomic group. R_ThreeAnd R_FourIs a Hammett substituent
Represents an electron-withdrawing group having a constant σp of 0.20 or more. However
Then R_ThreeAnd R_FourIs 0.65 or more. Z_Two
Is a nonmetallic atom necessary to form a nitrogen-containing 5-membered heterocyclic ring
Represents a group, and the 5-membered ring may have a substituent. X₁
And X_TwoIs a hydrogen atom or an oxidized form of a color developing agent, respectively.
Represents a group which is eliminated by a coupling reaction with ] 6. A silver halide light-sensitive material having a silver halide emulsion layer on a support is scanned and exposed in exposure units smaller than halftone dots, and then developed while replenishing in accordance with the amount of the silver halide light-sensitive material. An area gradation image forming method, wherein the silver halide photosensitive material is the silver halide photosensitive material according to any one of claims 1 to 5.