JPH05197064A - Direct positive silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain direct positive silver halide color photographic sensitive material suitable for forming a color proof improved in the approximation of image quality to a printed matter from the information of plural black-and- white dot images obtained by color separation and dot images conversion. CONSTITUTION:The direct positive silver halide color photographic sensitive material comprises a support, and at least each one of yellow, magenta, cyan, and black image-forming silver halide emulsion layers each containing internal latent image type silver halide grains. The spectral sensitivity of the black image-forming silver halide emulsion layer has common parts with each spectral sensitivity region of the yellow, magenta, and cyan image forming silver halide emulsion layers, and the black image forming layer contains at least one of N-containing heterocyclic compounds having a mercapto group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive silver halide color photographic light-sensitive material, and more specifically to a direct positive silver halide color photographic light-sensitive material suitable for producing a color image (color proof) for proof in a color plate making / printing process. Regarding

[0002]

BACKGROUND OF THE INVENTION Conventionally, diazo compounds and photopolymers have been used as a method for obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion in the process of color plate making / printing. An overlay method for forming a color image and a surprint method are known.

The overlay method is very simple and inexpensive to produce, and has the advantage that it can be used for proofreading by simply stacking four color (subtractive primary colors and black) film sheets. There is a drawback in that the overlapping produces gloss, which results in a texture different from that of the printed matter.

The surprint method is a method of superposing colored images on a single support. As this method, a method of obtaining a colored image by toner development utilizing the adhesive property of a photopolymerizable material is described in US Pat. No. 3,582,327. Nos. 3,607,264 and 3,620,726. A method of forming a color proof by transferring to a support using a photosensitive coloring sheet, forming an image by exposure and development, laminating another coloring sheet on this, and repeating the same process. Are known from JP-B-47-27441 and JP-A-56-501217. Further, a method of forming a single support by transferring each colored image obtained by exposing and developing each corresponding color separation film using a photosensitive colored sheet is known from JP-A-59-97140. Has been. As the colorant of the toner and the color sheet for forming these images, the same coloring material as the printing ink can be used, and thus the color tone of the obtained color proof becomes similar to that of the printed matter.

However, these methods have the drawbacks that images must be superposed or transferred in the process of producing a color proof, which requires a long operation time and high manufacturing cost.

By the way, in the recent plate making process, both the color separation and the halftone dot formation are automatically performed by using the electronic point formation type color separation scanning. The four halftone separated images have been electronically processed and separately imaged on a black and white silver halide film using a scanning laser system. Printing plates have been produced from these four silver images or their contact exposure copies. As a further development in this field, electronic page composers capable of handling digitally stored image data for the purpose of page formatting are increasingly used.

A highly desirable method associated with electronic scanners and page composers is a direct color proof from electronically stored data without the need to form intermediate black and white images on silver halide photographic film. It is a method of making impressions.

Several methods are already known for producing color proofs directly from electronically stored images, but none are satisfactory in quality, cost, handling and speed.

As a means for solving such a problem,
A silver salt color photographic light-sensitive material having a white support (hereinafter,
A method of making a color proof is also considered. Further, among the silver salt color photographic light-sensitive materials, it is advantageous to use a direct positive color light-sensitive material using internal latent image type silver halide grains in terms of color, reproduction stability and the like.

In these methods, a color-separated black-and-white halftone image consisting of a plurality of sheets converted from color originals into color-separated halftone images is successively printed on one sheet of color paper by a method such as contact printing, or After printing on color paper by direct scanning exposure from electronically stored data,
A color image formed by a dye formed from a coupler imagewise by color development is used as a proof image.

The method for forming a color proof using this color light-sensitive material is simple, quick, and low in cost.
This is a useful method because it is possible to obtain a finish close to that of a printed matter.

In this method, a black image forming layer, particularly a black image forming layer having a spectral sensitivity region common to the spectral sensitivity regions of the other three types of color forming layers, is formed in order to obtain a color proof that is more similar to a printed matter. By newly installing,
Attempts have been made to separate color image density from black image density.

However, if a new black image forming layer is provided, the density of the white background becomes high and the dot quality becomes worse, which makes practical application difficult. In particular, this tendency was remarkable in scanning exposure in which exposure was performed with relatively high illuminance.

[0014]

SUMMARY OF THE INVENTION Therefore, firstly, an object of the present invention is to directly obtain a color proof from a plurality of black and white halftone dot image information obtained by color separation and halftone dot image conversion using a positive silver halide color photographic light-sensitive material. An object of the present invention is to provide a color proof having an improved degree of approximation of image quality with a printed matter when manufactured. Secondly, it has photographic color image hue and black background similar to printed matter,
Moreover, it is to provide a color proof excellent in white background and halftone dot quality. Thirdly, it is to provide a color proof that has each of the separated hues and a black background similar to those of a printed matter and can be directly produced from digitally stored image data.

[0015]

The object of the present invention is to provide at least one layer of a yellow image forming property, a magenta image forming property, a cyan image forming property and a black image containing internal latent image type silver halide grains on a support. In a direct positive silver halide color photographic light-sensitive material having a formable silver halide emulsion layer, the spectral sensitivity of the black image forming silver halide emulsion layer is such that the yellow image forming property, magenta image forming property and cyan image forming halogen Achieved by a direct positive silver halide color photographic light-sensitive material having a common spectral sensitivity region of each silver halide emulsion layer and containing at least one nitrogen-containing heterocyclic compound having a mercapto group in the black image forming layer. Was done.

The present invention will be described in more detail below.

First, an internal latent image type direct positive silver halide emulsion which has not been fogged and is used in the present invention will be described.

The non-pre-fogged internal latent image type silver halide grain according to the present invention is a silver halide grain which mainly forms a latent image inside the silver halide grain and has most of the photosensitive nucleus inside the grain. Emulsions having grains in which any silver halide is used. Particularly preferably, a portion of the sample coated on a transparent support so that the amount of coated silver is in the range of about 1 to 3.5 g / m ² is applied for a certain period of time of about 0.1 second to about 1 second. Of the same emulsion sample when exposed to a light intensity scale for 4 minutes at 20 ° C. using the surface developer A described below which develops only the surface image of the grains containing substantially no silver halide solvent. An emulsion showing the maximum density which is not larger than 1/5 of the maximum density obtained by developing the image inside the grain by exposing another part in the same manner and developing for 4 minutes at 20 ° C. in the following internal developer B. is there. More preferably, the maximum density obtained using surface developer A is no greater than 1/10 of the maximum density obtained with internal developer B.

(Surface developer A) Metol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water was added 1000 ml (internal developer B) Metol 2.0 g Sodium sulfite (Anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water was added to 1000 ml. Those prepared by the method are included. For example US patent
Conversion type silver halide emulsions described in 2,592,250, or silver halide emulsions having internally chemically sensitized silver halide grains described in U.S. Patents 3,206,316, 3,317,322 and 3,367,778, or U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,53,291 contain emulsions having silver halide grains containing polyvalent metal ions, or contain the dopants described in U.S. Pat.No. 3,761,276. Silver halide emulsions whose surface is weakly chemically sensitized, or grains having a laminated structure described in JP-A Nos. 50-8524, 50-38525 and 53-2408. And a silver halide emulsion described in JP-A Nos. 52-156614 and 55-127549.

The internal latent image type silver halide grain in the present invention is a silver halide having an arbitrary halogen composition, for example, silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide, chloroiodo. It may be silver bromide. The grains containing silver chloride have excellent developability and are suitable for rapid processing.

The shapes of particles are cubic, octahedral, and (100) plane.
A tetrahedron composed of a mixture of (111) faces, a shape having a (110) face,
It may be spherical, flat, or the like. The average particle size is 0.
Those having a diameter of 05 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having uniform grain size and crystal habit, or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having uniform grain size and crystal habit. Is preferred. In the present invention, the monodisperse silver halide emulsion means that the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. The content is preferably 70% or more, more preferably 80% or more. Here, the average particle size r is the product n of the frequencies ni and ri3 of particles having the particle size r i.
It is defined as the grain size ri when i × ri3 becomes maximum. (3 significant digits, rounded down to the nearest digit.) The grain size referred to here is the diameter of a spherical silver halide grain,
Further, in the case of particles having a shape other than spherical, it is the diameter when the projected image is converted into a circular image having the same area. The particle size is, for example, taken by enlarging the particles from 10,000 times to 50,000 times with an electron microscope,
It can be obtained by measuring the particle diameter on the print or the area at the time of projection. (The number of measured grains is indiscriminately 1000 or more.) A particularly preferable highly monodisperse emulsion is (grain size standard deviation / mean grain size) × 100 = distribution defined by breadth of distribution (%) Is less than 20% wide. Here, the average particle size and the particle size standard deviation are obtained from ri defined above.

The monodisperse emulsion can be obtained by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed grains by the double jet method under the control of pAg and pH. In determining the addition rate,
The public relations of JP-A-54-48521 and JP-A-58-49938 can be referred to.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied.

The silver halide in the present invention can be optically sensitized by a commonly used sensitizing dye. It is also useful for the silver halide emulsion of the present invention to use a combination of sensitizing dyes used for supersensitization such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion. Regarding the sensitizing dyes, Research Disclosure (hereinafter abbreviated as RD) Nos. 15162 and 17643 can be referred to.

The nitrogen-containing heterocyclic compound having a mercapto group used in the present invention (hereinafter, also referred to as "mercapto compound of the present invention") is preferably a compound represented by the following general formula [I].

[0026]

[Chemical 1]

In the formula, M is a hydrogen atom, an alkali metal atom,
It represents a protective group for an ammonium group or a mercapto group, and Z represents a group of non-metal atoms necessary for forming a heterocycle. The heterocycle may have a substituent and may be condensed.

The protecting group for the mercapto group represented by M is a group which is cleaved by an alkali to form a mercapto group, and specific examples thereof include an acyl group, an alkoxycarbonyl group and an alkylsulfonyl group.

[0029]

[Chemical 2]

The heterocyclic group represented by is a carbon atom,
You may have a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, etc. as a ring constituent atom, and a 5- or 6-membered ring is preferable. Specific examples of the heterocycle include imidazole, benzimidazole, naphthimidazole, thiazole, thiazoline,
Benzothiazole, naphthothiazole, oxazole,
Examples thereof include benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, triazole, benzotriazole, tetrazole, oxadiazole, thiadiazole, pyridine, pyrimidine, triazine, purine and azaindene.

Examples of the substituent which these heterocycles may have include a halogen atom, hydroxyl, amino,
Examples thereof include groups such as nitro, mercapto, carboxyl and salts thereof, sulfo and salts thereof, alkyl, alkoxy, aryl, aryloxy, alkylthio, arylthio, acylamino, sulfonamide, carbamoyl and sulfamoyl.

Among the compounds represented by the general formula [I], the compounds particularly preferably used are the following general formulas [II] and [II
I] and [IV].

[0033]

[Chemical 3]

In the general formulas [II] to [IV], M has the same meaning as M in the general formula [I].

In the general formula [II], Ar is a phenyl group,
It represents a naphthyl group or a cycloalkyl group, and R ¹ represents a hydrogen atom or a substituent of Ar.

In the general formula [III], Z ¹ is an oxygen atom,
It represents a sulfur atom, a selenium atom or —NH—, and R ² represents a hydrogen atom or a substituent.

In the general formula [IV], Z ² is an oxygen atom,
Sulfur atom, selenium atom or ^{-N (R 4) - (R} 4 is a hydrogen atom,
Alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, -COR ^5, represents -SO ₂ R ^5, -NHCOR ⁶ or -NHSO ₂ R ^6, R ⁵ is an alkyl group, an aryl group, an aralkyl group, or Represents an amino group, R ⁶ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group), and R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocycle. Represents a group or an amino group.

The typical examples of the compounds represented by formula (I) are shown below, but the invention is not limited thereto.

[0039]

[Chemical 4]

[0040]

[Chemical 5]

[0041]

[Chemical 6]

[0042]

[Chemical 7]

[0043]

[Chemical 8]

The above compound can be easily synthesized by a known method. For example, U.S. Patents 2,403,927 and 3,3
76,310, JP-A-55-59463, or Journal of the Chemical Society (J.Chem.Soc.), 1952.
Yearly, it can be obtained according to the method described on page 4237. Also, some compounds are available as commercial products.

The mercapto compound of the present invention may be added to the light-sensitive material after being dissolved in water or an organic solvent having an affinity for water, such as methanol or acetone, or dissolved in a weak alkali or a weak acid. it can. The addition amount may be appropriately changed depending on the type of compound used and the layer to be added, and when it is added to the silver halide emulsion layer, it is generally within the range of 10 ^-8 to 10 ^-2 mol per mol of silver halide. , And more preferably 10 ⁻⁶ to 10 ⁻³ mol.

For the black image forming layer in the present invention, any conventionally known method can be used as long as a black image is formed after color development. For example, an image formed by storing a silver image after development processing can be used. It is also possible to use a black coupler which forms a black image by color development. Further, a black image can be obtained by mixing yellow, magenta and cyan couplers.

In the present invention, the black image forming layer has a spectral sensitivity region having a common portion with the spectral sensitivity region of the yellow image forming silver halide emulsion layer, and of the magenta image forming silver halide emulsion layer. It has a spectral sensitivity region having a common portion with the spectral sensitivity region, and further has a spectral sensitivity region having a common portion with the spectral sensitivity region of the cyan image forming silver halide emulsion layer.

In one preferred embodiment of the invention, for example, the yellow imaging layer contains a blue sensitive emulsion,
The magenta image forming layer contains a green-sensitive emulsion, the cyan image forming layer contains a red-sensitive emulsion, and the black image forming layer contains an emulsion sensitive to any of blue light, green light and red light.

Such an emulsion can be realized by selecting a spectral sensitizing dye. For example, an emulsion having sensitivity to any of blue light, green light, and red light as described above can be prepared, for example, by combining an emulsion having sensitivity to blue with a green-sensitizing dye and a red-sensitizing dye. .

In the color light-sensitive material of the present invention, it is used for at least three silver halide emulsion layers having different spectral sensitivities, and a silver halide emulsion layer having the same spectral sensitivity as the silver halide emulsion layers. The following can be used as the sensitizing dye.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent 929,080,
U.S. Patents 2,231,658, 2,493,748, 2,503,776
No., No. 2,519,001, No. 2,912,329, No. 3,656,959,
No. 3,672,897, No. 3,694,217, No. 4,025,349, No. 4,0
46,572, British Patent 1,242,588, Japanese Patent Publication No. 44-14030,
Examples thereof include those described in No. 52-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
72,908, 2,739,149, 2,945,763, British patent 50
Examples include those described in No. 5,979.

Further, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, US Pat. No. 2,269,23.
No. 4, No. 2,270,378, No. 2,442,710, No. 2,454,629,
Cyanine dyes such as those described in No. 2,776,280,
Representative examples are merocyanine dyes and complex cyanine dyes. Furthermore, US Pat. No. 2,213,99
No. 5, No. 2,493,748, No. 2,519,001, West German Patent 929,080
Cyanine dyes or complex cyanine dyes such as those described in JP-A No. 1994-242242 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

Infrared spectral sensitizing dyes are used as useful sensitizing dyes to be further used in the infrared spectrally sensitized silver halide emulsion. For example, JP-A Nos. 63-304242 and 63-123454.
No. 2, JP-A 1-293342, No. 2-40646, U.S. Pat.
Representative examples thereof include tricarbocyanine dyes and 4-carboline nucleus-containing dicarbocyanine dyes as described in Japanese Patent No. 76, British Patent 742,112, French Patent No. 2,065,662, and Japanese Patent Publication No. 40-2346.

The addition amount of the sensitizing dye used in the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers may vary in a wide range depending on the case, but is usually 1 × per mol of silver halide.
It can be used in the range of 10 ^-6 to 1 × 10 ^-2 mol, preferably 1 ×
It is 10 ⁻⁵ to 1 × 10 ⁻³ mol. The infrared sensitizing dye used in the infrared-sensitive silver halide emulsion is usually 2.5 × 10 ^{−7 to} 2.5 × 10 ⁻³ mol, preferably 2.5 × 1 mol per mol of silver halide.
It is in the range of 0 ^{−6 to} 2.5 × 10 ⁻⁴ mol.

As a dye which is used together with a sensitizing dye and has no spectral sensitizing effect, or a substance which does not substantially absorb visible light and exhibits supersensitization,
For example, an aromatic organic acid formaldehyde condensate (for example, those described in U.S. Pat. No. 3,473,510), a cadmium salt, an azaindene compound, and an aminostyryl compound substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat.
5,721)) etc. U.S. Patent 3,615,613
The combinations described in No. 3, No. 3,615,641, No. 3,617,295, No. 3,635,721, etc. are particularly useful.

In the emulsion layer of the color light-sensitive material according to the present invention, a dye-forming coupler capable of forming a dye by a coupling reaction with an oxidant of a color developing agent can be used.
The dye-forming couplers are usually selected for each emulsion layer so that a dye that absorbs the light in the light-sensitive spectrum of the emulsion layer is formed, and in the blue-sensitive emulsion layer the yellow dye-forming coupler is the green dye. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, the color light-sensitive material may be produced by a method different from the above combination depending on the purpose.

These dye-forming couplers preferably have a group called a ballast group having a carbon number of 8 or more, which makes the coupler non-diffusible, in the molecule. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye. Even if they are 4-equivalent, only 2 molecules of silver ions need to be reduced. Either equivalence may be used. Releases a development inhibitor along with development, releases a development inhibitor at the same time as a DIR coupler that improves image sharpness and image graininess, and produces a colorless compound by coupling reaction with an oxidized product of a developing agent. DIR compounds may be used.

The DIR coupler and the DIR compound used have an inhibitor bound directly to the coupling position and an inhibitor bound to the coupling position via a divalent group, and are released by the coupling reaction. Those which are bonded so as to release the inhibitor by intramolecular nucleophilic reaction, intramolecular electron transfer reaction and the like (referred to as timing DIR coupler and timing DIR compound) are included.

A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine type developer but does not form a dye can be used in combination with the dye-forming coupler.

Known acylacetanilide type couplers can be preferably used as the yellow dye-forming coupler. Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous, but as the yellow coupler used in the present invention, a coupler represented by the following general formula (Y-1) is particularly preferable. Is obtained and is preferable.

[0061]

[Chemical 9]

In the formula, R ₁ represents an alkyl group, a cycloalkyl group or an aryl group, R ₂ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, and R ₃ represents a group capable of substituting on the benzene ring. Represent n represents 0 or 1. X
₁ represents a group capable of reacting with an oxidized product of a developing agent upon coupling and leaving, and Y ₁ represents an organic group.

Examples of the alkyl group represented by R ₁ include groups such as methyl, ethyl, i-propyl, t-butyl and dodecyl. The alkyl group represented by R ₁ further includes those having a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group,
Examples thereof include a hydroxyl group.

Examples of the cycloalkyl group represented by R ₁ include cyclopropyl, cyclohexyl and the like, as well as organic hydrocarbon residues in which two or more cycloalkyls are condensed (for example, adamantyl and the like). The cycloalkyl group represented by R ₁ includes those having a substituent, and examples of the substituent include those exemplified as the substituent of the alkyl group represented by R ₁ .

Examples of the aryl group represented by R ₁ include a phenyl group and the like, and the aryl group includes those having a substituent. Examples of the substituent include those exemplified as the substituent of the alkyl group represented by R ₁ and the alkyl group. R ₁ is preferably a branched alkyl group.

Examples of the alkyl group, cycloalkyl group and aryl group represented by R ₂ include the same groups as R ₁ and include those each having a substituent. Examples of the substituent include those exemplified for R ₁ . Examples of the acyl group include acetyl, propionyl, butyryl, hexanoyl and benzoyl groups, and the acyl group includes those having a substituent. R ₂ is preferably an alkyl group or an aryl group, more preferably an alkyl group, and most preferably a lower alkyl group having 5 or less carbon atoms.

The group capable of substituting the benzene ring represented by R ₃ includes a halogen atom (eg chlorine), an alkyl group (eg ethyl, i-propyl, t-butyl etc.), an alkoxy group (eg methoxy). , Aryloxy group (eg phenyloxy), acyloxy group (eg acetyloxy, benzoyloxy etc.), acylamino group (eg acetamide, benzamide etc.), carbamoyl group (eg N-methylcarbamoyl, N-phenylcarbamoyl etc.) alkylsulfonamide Groups (eg ethyl sulfonamide), aryl sulfonamide groups (eg phenyl sulfonamide), sulfamoyl groups (eg N-propylsulfamoyl, N-phenylsulfamoyl etc.) and imide groups (eg succinimide, glutarimide etc.)
Is mentioned.

The organic group represented by Y ₁ is preferably a group represented by the following general formula (Y-2).

In the general formula (Y-2)-(J) p-R ₄ , R ₄ represents an organic group containing one bonding group having a carbonyl or sulfonyl unit. p represents 0 or 1.

Examples of the group having a carbonyl unit include an ester group, an amide group, a carbamoyl group, a ureido group and a urethane group. Examples of the group having a sulfonyl unit include a sulfonyl group, a sulfonylamino group, a sulfamoyl group and an aminosulfonyl group. An amino group etc. are mentioned.

J represents --N (R ₅ ) CO--, R ₅ is a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group.

Examples of the alkyl group represented by R ₅ include methyl, ethyl, i-propyl, t-butyl and dodecyl. Examples of the aryl group represented by R ₅ include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by R ₅ include a pyridyl group.

Each of the groups represented by R ₅ includes those having a substituent. The substituent is not particularly limited, but a typical example is a halogen atom (chlorine, etc.),
Alkyl group (ethyl, t-butyl, etc.), aryl group (phenyl, p-methoxyphenyl, naphthyl, etc.), alkoxy group (ethoxy, benzyloxy, etc.), aryloxy group (phenoxy, etc.), alkylthio group (ethylthio, etc.),
Arylthio group (phenylthio, etc.), alkylsulfonyl group (β-hydroxyethylsulfonyl, etc.), arylsulfonyl group (phenylsulfonyl, etc.), acylamino group (alkylcarbonylamino group such as acetamide, arylcarbonylamino group such as benzamide), carbamoyl group (Alkylcarbamoyl group such as N-methylcarbamoyl, arylcarbamoyl group such as N-phenylcarbamoyl), acyl group (alkylcarbonyl group such as acetyl, arylcarbonyl group of benzoyl group), sulfonamide group (alkyl such as methylsulfonamide) Sulfonamide group, arylsulfonamide group such as phenylsulfonamide), sulfamoyl group (alkylsulfamoyl group such as N-methylsulfamoyl, aryl such as N-phenylsulfamoyl) Rufamoiru group), a hydroxyl group, a cyano group, and the like.

Examples of the group represented by the formula (Y-3) or the general formula (Y-4) shown below are groups which are released during the coupling reaction with the oxidized product of the developing agent represented by X _1. , And particularly preferably a group represented by the general formula (Y-4).

[0075] In formula (Y-3) -OR ₆ formula, R ₆ represents an aryl group or a heterocyclic group include those having a substituent.

[0076]

[Chemical 10]

In the formula, Z ₁ represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring in cooperation with a nitrogen atom. Examples of the atomic group include substituted or unsubstituted methylene, methine, and
C = O, -NR _A ( _RA has the same meaning as R ₅ ), -N =,-
O -, - S -, - SO 2 - , and the like.

The yellow coupler represented by the general formula (Y-1) may be bonded at R ₁ , R ₃ or Y ₁ part to form a bis form.

Particularly preferable as the yellow coupler of the present invention is a compound represented by the following general formula (Y-5).

[0080]

[Chemical 11]

In the general formula (Y-5), R ₁ , R ₂ and R
₃ , n and J are R ₁ , R ₂ in the general formula (Y-1),
It has the same meaning as R ₃ and n and J and p in the general formula (Y-2), and the same ones are exemplified. R ₇ is an alkylene group, an arylene group, an alkylenearylene group, an arylenealkylene group or -A-V ₁ -B- (A and B are respectively
Represents an alkylene group, an arylene group, an alkylenearylene group or an arylenealkylene group, V ₁ represents a divalent linking group), and R ₈ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. P represents a bonding group having a carbonyl or sulfonyl unit. X ₂ represents a group capable of splitting off upon coupling with an oxidized product of a developing agent.

Examples of R ₇ and A or the alkylene group represented are, for example, methylene, ethylene, trimethylene, butylene, hexylene, methylmethylene, ethylethylene, 1-
Examples thereof include linear or branched ones such as methylethylene, 1-methyl-2-ethylethylene, 2-decylethylene and 3-hexylpropylene. The alkylene group includes those having a substituent (for example, an aryl group), and examples thereof include groups such as 1-benzylethylene, 2-phenylethylene, and 3-naphthylpropylene.

Examples of the arylene group include phenylene and naphthylene, and the arylene group includes those having a substituent.

Examples of the alkylenearylene group include methylenephenylene and the like, and examples of the arylenealkylene group include phenylenemethylene and the like, and those having respective substituents are included.

The divalent linking group represented by V ₁ is --O.
Examples thereof include groups such as-and -S-.

Of the alkylene group, arylene group, alkylenearylene group, arylenealkylene group and -A-V ₁ -B-represented by R ₇ , an alkylene group is particularly preferable.

Examples of the alkyl group represented by R ₈ include linear or branched ones such as ethyl, butyl, hexyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, 2-hexyldecyl and octadecyl. Examples of the cycloalkyl group include cyclohexyl and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include pyridyl and the like.

The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₈ further include those having a substituent, and the substituent is not particularly limited, and the substituent of R ₅ is What was illustrated as a group can be mentioned. However, the pKa value for the substituent of R ₈ is
Organic groups having a dissociative hydrogen atom of 9.5 or less (for example, a phenolic hydrogen atom) are preferred.

P represents a bonding group having a carbonyl or sulfonyl unit, preferably a group represented by the following group (Y-6), and preferably a bonding group represented by (6) to (9).

Group (Y-6) (1) -COO-, (2) -N (R) CO-, (3) -CON (R)
−, (4) −N (R) CON (R ′) −, (5) −N (R) COO−
_{(6) -SO 2 -, (} 7) -N (R) SO 2 - (8) -SO 2 N (R) -,
(9) —N (R) SO ₂ N (R ′) — In the formula, R and R ′ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Examples of the group represented by R and R ′ include the groups exemplified for R ₅ above.
Further, these groups include those having a substituent. Examples of the substituent include those exemplified as the R ₅ substituent. R and R'are preferably hydrogen atoms.

The yellow coupler represented by the general formula (Y-1) of the present invention is preferably 1 × 10 ⁻³ to 1 mol, and more preferably 1 × 10 ⁻² to 8 ×, per mol of silver halide.
It can be used in the range of 10 ^-1 mol.

As the magenta dye-forming coupler, known 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers, open chain acylacetonitrile type couplers, indazolone type couplers and the like can be used. In particular, the magenta coupler represented by the following general formula [MI] is
It is preferable that a hue closer to printing can be obtained by printing.

[0093]

[Chemical 12]

In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent.

In the above general formula [MI], the substituent represented by R is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl. Other groups such as halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, and the like. Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro. A compound residue, a bridged hydrocarbon compound residue, etc. are also mentioned.

The substituent represented by R, the group capable of splitting off by the reaction with the oxidized product of the color developing agent represented by X, the nitrogen-containing heterocycle formed by Z and the ring formed by Z may have. The preferred range and specific examples of the substituents, and the preferred range of the magenta coupler represented by the general formula [MI] are the same as those described in EP 0327272, page 5, line 23 to page 8, line 52. ..

As another specific example, European Patent Publication 0273
Compounds M-1 to M-6 described in No. 712, pages 6 to 21.
1 and Compound 1 described in No. 0235913, pages 36 to 92
~ 223 other than the above representative examples.

Further, the coupler is a Journal of the Chemical Society.
ciety), Perkin I (1977), 2047-2052, US Pat. No. 3,725,067, JP-A-59-99437, 58-42045.
No. 59, No. 162548, No. 59-171956, No. 60-33552, No. 60-33552
60-43659, 60-172982, 60-190779, 62-20945
It can be synthesized with reference to No. 7 and No. 63-307453.

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

As the cyan dye forming coupler, known phenol type, naphthol type or imidazole type couplers can be used. Typical examples are phenol-based couplers substituted with an alkyl group, an acylamino group, or a ureido group, naphthol-based couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol-based couplers having an oxygen atom introduced as a leaving group. To be done.

In the present invention, any conventionally known coupler can be used in the black image forming layer as long as a black image is formed after color development. For example, a black coupler that forms a black image by color development can be used. Further, a black image can be obtained by mixing yellow, magenta and cyan couplers. Particularly, from the viewpoint of controlling the color tone of a black image, a configuration in which yellow, magenta, and cyan couplers are mixed is effective.

The coupler used can be selected from the above-mentioned couplers and may be the same as or different from the couplers used in the other image forming layers.

The yellow image forming layer, the magenta image forming layer, the cyan image forming layer and the black image forming layer of the present invention are laminated and coated on a support, but the order from the support may be any order. One preferred embodiment is, for example, a cyan image forming layer, a magenta image forming layer, a yellow image forming layer, and a black image forming layer from the side closer to the support. In addition to these, an intermediate layer, a filter layer, a protective layer and the like can be arranged as required.

Known photographic additives can be used in the light-sensitive material of the present invention. Known photographic additives include, for example, the compounds described below in RD17643 and RD18716.

Additives RD17643 RD18716 Page classification Page classification Chemical sensitizer 23 III 648 Upper right sensitizing dye 23 IV 648 Upper right development accelerator 29 XXI 648 Upper right antifoggant 24 VI 649 Lower right stabilizer Stabilization 〃 Color staining prevention Agent 25 VII 650 Left-right Image stabilizer 25 VII UV absorber 25-26 VII 649 Right-650 left Filter dye 〃 〃 Whitening agent 24 V Hardener 26 X 651 Right Coating aid 26-27 XI 650 Right interface Activator 26-27 XI 650 Right Plasticizer 27 XII 650 Right Sliding agent 〃 〃 Static inhibitor 〃 〃 Matting agent 28 XVI 650 Right binder 29 IX 651 Right As the support that can be used in the photosensitive material of the present invention, Examples thereof include those described on page 28 of RD17643 and page 647 of RD18716. Suitable supports are polymer films, papers and the like, which may be treated for enhancing the adhesiveness, antistatic property and the like.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam, X ray, γ ray Any of known light sources such as light emitted from a phosphor excited by α-ray or the like can be used.

The exposure time is usually 10 for a printer.
^-3 seconds to 10 seconds exposure time, as well as exposure shorter than 10 ^-3 seconds, such as 10 ^-6 -10 using a cathode ray tube or xenon flashlight
^-3 second exposures can be used or exposures longer than 10 seconds are possible. The exposure may be performed continuously or intermittently.

For example, the color light-sensitive material of the present invention is used as a decomposition filter using Ratten No. 58, No. 61, N0.47B,
A three-wavelength fluorescent tube is used as a light source, and exposure can be performed for 10 ^-1 second to several seconds.

However, the effect of the present invention is remarkably exhibited by the so-called scanning type exposure apparatus which scans the light beam on the surface of the photosensitive material.

In this scanning exposure apparatus, three types of light sources B, G,
Those using R are known. As the light source, a combination of a white light source lamp such as a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp and a filter,
Light emitting diodes, gas lasers, solid-state lasers, semiconductor lasers and the like are known, and laser light having a narrow output light intensity distribution is particularly preferable. Also, a combination of various lasers and a wavelength conversion element may be used, and a combination of an infrared semiconductor laser and an SHG element is preferable from the viewpoint of compactness.

As specific examples, He-Cd gas laser (441.6 nm), Ar ⁺ laser (488.0 nm), He-Ne as blue light are used.
He-Ne gas laser (543.5nm), Ar ⁺ gas laser (514.5nm), K as green light such as gas laser (442.0nm)
He ⁺ Ne as red light such as r ⁺ gas laser (520.8 nm), YAG laser or infrared semiconductor laser in combination with SHG element
Gas laser (632.8nm), Kr ⁺ gas laser (647.1n
m), semiconductor laser (678nm) (750nm) (780nm), etc. When a He-Ne gas laser is used as a light source, it becomes a stable, inexpensive, and compact device. It is also possible to obtain a plurality of oscillations from one He-Ne gas laser and use them separately with a dichroic mirror or the like. For example, one He-Ne
Four oscillation lines from gas laser (442nm, 543.5nm, 59
4.1nm, 632.8nm) and so on.

The photographic light-sensitive material having a silver halide emulsion layer according to the present invention forms a positive image directly by subjecting it to image development followed by development with fog. The fog treatment can be carried out by using a compound that gives an overall exposure or generates a fog nucleus, that is, a fog agent.

The whole surface exposure is carried out by immersing the imagewise exposed light-sensitive material in a developing solution or other aqueous solution or moistening it and then uniformly exposing the whole surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the photosensitive material,
High illuminance light such as flash light may be applied for a short time, or weak light may be applied for a long time.

The exposure time of the entire surface can be varied within a wide range so that the best positive image can be finally obtained depending on the above-mentioned light-sensitive material, development processing conditions, kind of light source used and the like.

Further, it is most preferable that the exposure amount of the whole surface exposure gives a predetermined range of exposure amount in combination with the photosensitive material. Usually, when an excessive exposure amount is given, the minimum density is increased or desensitized, and the image quality tends to be deteriorated.

Next, the fog agent preferably used in the present invention will be described.

A wide variety of compounds can be used as the fog agent used in the present invention, and the fog agent only needs to be present at the time of development processing. In particular, it is preferably in a silver halide emulsion layer), or in a developing solution or a processing solution prior to the developing processing. The amount used can be varied over a wide range according to the purpose, and the preferable addition amount is as follows when it is added to the silver halide emulsion layer.
1 to 1500 mg, preferably 10 to 1 mol per mol of silver halide
It is 1000 mg. When it is added to a processing solution such as a developing solution, the preferable addition amount is 0.01 to 5 g per liter of the processing solution,
It is particularly preferably 0.05 to 1 g.

Examples of the fogging agent used in the present invention include hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982 or hydrazides or hydrazine compounds described in US Pat. No. 3,227,552; US Pat.
5, 3,718,479, 3,719,494, 3,734,738 and 3,759,901, heterocyclic quaternary nitrogen salt compounds; further silver halides such as acylhydrazinophenylthioureas described in U.S. Pat. No. 4,030,925. Examples thereof include compounds having an adsorption group on the surface. Further, these fogging agents can be used in combination. For example, RD1516 described above
No. 2 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, or they can be used in combination. Specific examples of useful fogging agents include hydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-acetyl-2-phenylhydrazine, 1-formyl-2- (4-methylphenyl) hydrazine, 1-methylsulfonyl. -2-phenylhydrazine, 1-methylsulfonyl-
2- (3-phenylsulfonamidophenyl) hydrazine, 1-
Hydrazine compounds such as benzoyl-2-phenylhydrazine and formaldehydephenylhydrazine; 3- (2-formylethyl) -2-methylbenzothiazolium bromide,
3- (2-acetylethyl) -2-benzyl-5-phenylbenzoxazolium bromide, 3- (2-acetylethyl) -2-benzylbenzoselenazolium bromide, 2-methyl-3-
[3- (phenylhydrazino) propyl] benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] benzothiazolium bromide, 1,2-dihydro-3- Methyl-4-phenylpyrido [2,1-b] benzoselenazolium bromide, 4,4′-ethylenebis (1,2-dihydro-
N-substituted quaternary cycloammonium salts such as 3-methylpyrido [2,1-b] benzothiazolium bromide; 5- (3-ethyl-
2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] rhodamine, 1,3-bis [4- (2-formylhydrazino) phenyl] thiourea, 7- (3- Ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl
-1,2,3,4-ratrahydroacridinium trifluoromethanesulfonate, 1-formyl-2- [4- {3- (2-methoxyphenyl) ureido} phenyl] hydrazine and the like can be mentioned.

The developer which can be used in the developer used for developing the photographic light-sensitive material according to the present invention is:
Conventional silver halide developers, for example, polyhydroxybenzenes such as hydroquinone, aminophenols, 3-
Pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or mixtures thereof are included. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N -(β-Methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline Etc. It is also possible to incorporate these developers in the emulsion in advance so that they act on the silver halide during immersion in a high pH aqueous solution.

The developer used in the present invention may further contain a specific antifoggant and development inhibitor, or these developer additives may be optionally incorporated in the constituent layers of the photographic light-sensitive material. Is also possible.

The light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as a bleaching agent, but among them, iron (III), cobalt (III), copper (II) and other polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, Nitrilotriacetic acid, aminopolycarboxylic acids such as N-hydroxyethylethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid or ferricyanates, dichromates, etc. A single one or a suitable combination is used.

As the fixing agent, a soluble complexing agent which solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.

After the fixing process, a washing process is usually performed. Further, a stabilizing treatment may be performed as an alternative to the water washing treatment, or both may be used in combination. The stabilizing solution used for the stabilizing treatment may contain a pH adjusting agent, a chelating agent, an antifungal agent and the like. These specific conditions are described in JP-A-58-1
You can refer to No. 34636.

[0124]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KB in molar ratio).
An aqueous solution containing r: NaCl = 95: 5) was simultaneously added by the control double jet method to obtain a cubic silver chlorobromide core emulsion having a grain size of 0.30 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. To the obtained core emulsion, an aqueous solution further containing ammonia and silver nitrate,
Potassium bromide and sodium chloride (molar ratio KBr: NaCl
= 40: 60) was simultaneously added by the control double jet method to form a shell until the average particle size became 0.42 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Blue Sensitive Emulsion EM-B) After sensitizing EM-1 with sensitizing dye D-1, T-1 was added at 60 per mol of silver.
0 mg was added to prepare a blue-sensitive emulsion EM-B.

(Preparation of Green Sensitive Emulsion EM-G) EM-1
A green-sensitive emulsion EM-G was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dye D-2 was added for color sensitization.

(Preparation of Red Sensitive Emulsion EM-R) EM-1
A red-sensitive emulsion EM-R was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dye D-3 was added for color sensitization.

(Preparation of pan-sensitive emulsion EM-P) EM-1
A sensitizing dye EM-P was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dyes D-1, D-2 and D-3 were added thereto for color sensitization.

T-1: 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene

[0132]

[Chemical 13]

Using the above EM-B, EM-G and EM-R,
First to tenth layers were applied to the surface of a support laminated on both sides with polyethylene in the following constitution to prepare a color light-sensitive material. The coating amount is shown in g / m ² , and the coating silver amount is a silver conversion value.

Layer composition Coating amount 10th layer Gelatin 0.78 (UV absorbing layer) UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.195 Solvent (SO-2) 0.1 Colloidal silica 0.03 9th layer Gelatin 1.43 (Blue sensitive layer) Blue sensitive emulsion EM-B (Coating silver amount) 0.5 Yellow coupler (YC-1) 0.82 Anti-staining agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-1, T-1) Eighth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Seventh layer Gelatin 0.42 (Yellow yellow colloidal silver 0.1 Colloidal silver layer) Anti-color mixing agent (AS- 1) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 6th layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 5th layer Gelatin 1.43 (Green feeling) Layer) A feeling of green Emulsion EM-G (Amount of coated silver) 0.50 Magenta coupler (MC-1) 0.25 Anti-staining agent (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-1, T-1) No. 4 Layer Gelatin 0.75 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.38 (Red sensitive layer) Red sensitive emulsion EM-R (Coating silver amount) 0.30 Cyan coupler (CC- 2) 0.44 Solvent (SO-1) 0.31 Anti-stain agent (AS-2) 0.015 Inhibitor (ST-1, T-1) Second layer Gelatin 0.54 (Intermediate layer) Color mixture inhibitor (AS-1) 0.055 Solvent ( SO-2) 0.072 1st layer gelatin 0.60 (halation black colloidal silver 0.10 prevention layer) SA-1 and SA-2 were used as coating aids, and AI-1 and AI-2 were used as irradiation prevention dyes.
Sample-1 was prepared using H-1 as a hardener.

The structural formulas of the compounds used are shown below.

SO-1: trioctyl phosphate SO-2: dioctyl phthalate AS-1: 2,5-di-t-octylhydroquinone AS-2: 2,5-di-t-butylhydroquinone ST-1: N- Benzyl adenine SA-1: sulfosuccinic acid di (2-ethylhexyl) ester / sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester / sodium H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium

[0137]

[Chemical 14]

[0138]

[Chemical 15]

In the same manner as in Sample-1, the EM-
Using B, EM-G, EM-R and EM-P, a color light-sensitive material sample-2 having the following constitution was prepared. (Coating amount is g / m ² ) Layer composition Coating amount 12th layer Gelatin 0.78 (UV absorbing layer) UV absorber (UV-1) 0.065 UV absorbing layer (UV-2) 0.195 Solvent (SO- 2) 0.1 Colloidal silica 0.03 11th layer Gelatin 1.05 (pan-sensitive layer) Pan-sensitive emulsion EM-P (coating silver amount) 0.30 Yellow coupler (YC-1) 0.21 Magenta coupler (MC-1) 0.063 Cyan coupler (CC-1) ) 0.110 Anti-staining agent (AS-2) 0.019 Solvent (SO-1) 0.615 10th layer gelatin 0.75 (intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 9th layer gelatin 1.14 (blue) Sensitive layer) Blue-sensitive emulsion EM-B (coating silver amount) 0.4 Yellow coupler (YC-1) 0.656 Anti-stain agent (AS-2) 0.02 Solvent (SO-1) 0.656 Inhibitor (ST-1, T-1) Eighth layer Gelatin 0.54 (intermediate layer) Color mixing prevention (AS-1) 0.055 Solvent (SO-2) 0.072 7th layer Gelatin 0.42 (Yellow yellow colloidal silver 0.1 colloidal silver layer) Color mixture inhibitor (AS-1) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 Sixth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Fifth layer Gelatin 1.14 (Green sensitive layer) Green sensitive emulsion EM-G (Amount of coated silver) 0.40 Magenta coupler (MC-1) 0.20 Anti-stain agent (AS-2) 0.0152 Solvent (SO-1) 0.248 Inhibitor (ST-1, T-1) Fourth layer Gelatin 0.75 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.10 (Red-sensitive layer) Red-sensitive emulsion EM-R (Coating silver amount) 0.24 Cyan coupler (CC-2) 0.352 Solvent (SO-1) 0.248 Anti-stain agent (AS) -2) 0.012 inhibitor (ST- , T-1) Second layer gelatin 0.54 (intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 First layer gelatin 0.60 (Halation black colloidal silver 0.10 prevention layer) Same as Sample-2 The compound shown in Table 1
Samples 3 to 8 added in 11 layers (generalized layer) were prepared.
For each sample, a black plate and a cyan plate among halftone originals were brought into close contact with each other and exposed under the following exposure condition-1. Next, the black plate and the magenta plate were brought into close contact with the sample and exposed under exposure condition -2. Furthermore, stick the black plate and the yellow plate to the sample,
Exposure was performed under exposure condition-3.

The exposed light-sensitive material was processed by the following development processing steps, the density of the obtained image was measured, and further compared with the density of the proof print obtained from the halftone original document 4th plate. .. In addition, color approximation, black approximation, and dot quality were also compared with proof printing.

The obtained results are also shown in Table 1. The density was measured using a Macbeth 914 densitometer and SPI filter.

(Exposure condition-1) When exposing each light-sensitive material to white light through a red filter (Ratten No. 26) and an ND filter, the ND filter density is adjusted to minimize the red light density after development processing. The minimum exposure dose is 0.5 seconds.

(Exposure condition-2) When exposing each light-sensitive material to white light through a green filter (Ratten No.58) and an ND filter, the ND filter density is adjusted to minimize the green light density after development processing. The minimum exposure dose is 0.5 seconds.

(Exposure condition-3) When exposing the white light through each light-sensitive material through a blue filter (Ratten No. 47B) and an ND filter, the ND filter density is adjusted to minimize the green light density after development processing. The minimum exposure dose is 0.5 seconds.

A daylight fluorescent lamp was used as the light source under the exposure conditions-1 to 3.

In the fog exposure during the following processing steps, the surface of the photosensitive material was uniformly exposed through the layer of the developing solution having a thickness of 3 mm while being immersed in the developing solution.

Processing Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds (1 lux) Image 37 ° C 95 seconds Bleach-fixing 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Dry 60-85 ℃ 40 seconds Treatment liquid composition is as follows.

Color developing solution Benzyl alcohol 15 ml Cerium sulfate 0.015 g Ethylene glycol 8.0 ml Potassium sulfite 2.5 g Potassium bromide 0.6 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g Diethylenetriamine pentasodium acetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Diethylene glycol 15.0ml Water In addition, adjust the total volume to 1 liter and adjust the pH to 10.15.

Bleach-fixing solution Diethylenetriamine 5 ferric ammonium acetate 90.0 g Diethylenetriamine 5 acetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1,2,4-triazole 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1 liter.

Stabilizing solution o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate 7-hydrate 0.7 g Hydroxylation Ammonium (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide or sulfuric acid. Adjust the pH to 7.5 with. The stabilization treatment was a countercurrent system with a two tank structure.

[0151]

[Table 1]

As is clear from the results shown in Table 1, Comparative Sample-1 does not satisfy both color approximation and black approximation. Comparative sample-2 has a low monochromatic density of the color image and a high black density, so that it is closer to proof printing (printing) in terms of hue, but is inferior in black dot density and white background density. On the other hand, Samples-3, 4,5, 7 and 8 according to the present invention have a hue of a color image, a hue of a black image and halftone dots which are close to those of a printed matter, and have a low white background density, which is excellent in overall quality. I understand that

Example 2 Samples 1 to 6 were subjected to scanning exposure using the following light source and wavelength instead of the exposure of Example 1, and thereafter, Example 1 was performed.
The development processing was performed and density measurement evaluation was performed in the same manner as in. The results are shown in Table 2.

Blue light He-Cd gas laser (441.6 nm) Green light He-Ne gas laser (543.5 nm) Red light He-Ne gas laser (632.8 nm)

[0155]

[Table 2]

As is clear from the results of Table 2, Example 1
Similarly to the comparative example, the present invention is superior in overall quality because the hue of the color image, the hue of the black image and the dot quality are closer to those of the printed matter, and the white background density is low. The effect is also remarkable in the scanning exposure of the second embodiment.

Example 3 (Preparation of Emulsion EM-2) An equimolar silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously added to a gelatin aqueous solution at 50 ° C. for 50 minutes by the double jet method to give an average particle size of 0.3.
An emulsion consisting of cubic silver bromide grains was obtained. To this emulsion, 6.5 mg of sodium thiosulfate and 3 mg of potassium chloroaurate were added per 1 mol of silver, and the mixture was chemically ripened at 70 ° C. for 70 minutes. 1: 9) is added at the same time, and the average particle size is
A cubic core / shell emulsion consisting of a 0.45 μm silver bromide core and a silver chlorobromide shell was prepared. After desalting with water, 2.0 mg of sodium thiosulfate and 1.0 mg of potassium chloroaurate were added to 1 mol of silver and chemically ripened at 60 ° C. for 50 minutes to obtain a direct positive silver halide emulsion EM-. Got 2.

(Preparation of Green Sensitive Emulsion EM-2G) EM-2
After the color sensitization by adding the sensitizing dye D-2 to the above, 600 mg of T-1 was added per mol of silver, and FA-1 and FA-2 were further added at 8 × 10 ⁻⁵ mol and 5 mol per mol of silver, respectively. × 10 ^-4 mol was added to prepare a green sensitive emulsion EM-2G.

(Preparation of Red Sensitive Emulsion EM-2R) EM-2
A red-sensitive emulsion EM-2R was prepared in the same manner as the green-sensitive emulsion except that the sensitizing dye D-3 was added for color sensitization.

(Preparation of infrared-sensitive EM-2I) EM-2
An infrared-sensitive emulsion EM-2I was prepared in the same manner as the green-sensitive emulsion except that the sensitizing dye D-4 was added for color sensitization.

(Preparation of pan-sensitive emulsion EM-2P) EM-2
In addition to sensitizing dyes D-2, D-3 and D-4 for color sensitization, a general-purpose emulsion EM-2P was prepared in the same manner as the green-sensitive emulsion.
Was produced.

[0162]

[Chemical 16]

Using the above EM-2G, EM-2R, EM-2I and emulsion EM-2P, the first to tenth layers having the following constitutions were formed on the surface of a support laminated on both sides with polyethylene.
To prepare a color photographic material sample -10 was coated in the same manner as Sample -1 Example 1 (amount with coating also indicated in g / m ^2, a silver halide emulsion of silver converted value). Coating aid SA-1, SA
-2, the use of the anti-irradiation dyes AI-1, AI-2 and the hardener H-1 is the same as in Sample-1.

Layer composition Coating amount 10th layer Gelatin 0.78 (UV absorbing layer) UV absorbing agent (UV-1)
0.065 Ultraviolet absorbing layer (UV-2) 0.195 Solvent (SO-2) 0.1 Colloidal silica 0.03 9th layer Gelatin 1.05 (pan sensitive layer) Pan-sensitive emulsion EM-2P (coating silver amount) 0.30 Yellow coupler (YC-1) ) 0.21 Magenta coupler (MC-1) 0.063 Cyan coupler (CC-1) 0.110 Stain inhibitor (AS-2) 0.019 Solvent (SO-1) 0.615 Eighth layer gelatin 0.75 (Intermediate layer) Color mixture inhibitor (AS-1) ) 0.055 Solvent (SO-2) 0.072 7th layer Gelatin 1.14 (Green sensitive layer) Green sensitive emulsion EM-2G (Amount of coated silver) 0.4 Yellow coupler (YC-1) 0.656 Anti-staining agent (AS-2) 0.02 Solvent ( SO-1) 0.656 Inhibitor (ST-1, T-1) Sixth layer Gelatin 0.75 (Intermediate layer) Color mixture inhibitor (AS-1) 0.055 Solvent (SO-2) 0.072 Fifth layer Gelatin 1.14 (Red sensitive layer) ) Red-sensitive emulsion EM-2R (Amount of coated silver) 0.40 Magenta coupler (MC-1) 0.20 Anti-staining agent (AS-2) 0.0152 Solvent (SO-1) 0.248 Inhibitor (ST-1, T-1) 4th layer Gelatin 0.75 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.10 (infrared photosensitive layer) Infrared photosensitive emulsion EM-2I (coating silver amount) 0.24 Cyan coupler (CC-2) 0.352 Solvent (SO-1) 0.248 Anti-staining agent (AS-2) 0.012 Inhibitor (ST-1, T-1) Second layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 1st layer gelatin 0.60 (halation black colloidal silver 0.10 prevention layer) Sample-11 was prepared in exactly the same manner as Sample-10 except that the compounds shown in Table 3 were added to the 9th layer (generalized layer). ~ 14 were made.

Each sample obtained as described above was subjected to scanning exposure using the following light source and wavelength, and the obtained exposed light-sensitive material was processed according to the following developing treatment step-2 to obtain The densities of the obtained dye images were measured and compared with the densities of the proofs obtained from 4th original halftone dots. The Macbeth 914 densitometer and SPI filter were used for the concentration measurement as in Example 1.

Green light He-Ne gas laser (543.5nm) Red light He-Ne gas laser (632.8nm) Infrared light Semiconductor laser (750nm) Treatment process-2 Temperature time Image 37 ℃ 130 seconds Bleach fixing 35 ℃ 45 Second stabilizing treatment 25 to 30 ° C. 90 seconds Drying 60 to 85 ° C. 40 seconds The formulations of the developing solution, the bleach-fixing solution and the stabilizing solution used here were the same as those used in Example 1, respectively. .. The stabilization process was also a countercurrent system with a two-tank configuration.

[0167]

[Table 3]

As is clear from the results of Table 3, Example 2
Similarly to the comparative example, the present invention is similar to the comparative example in the hue of the color image, the hue of the black image, and the dot quality, and the white background density is low, which is excellent in overall quality.

[0169]

EFFECT OF THE INVENTION By using the direct positive silver halide color photographic light-sensitive material of the present invention, a color proof having an excellent degree of approximation of image quality to a printed matter can be obtained by three times of exposure. Also, a color proof with excellent image quality was obtained by scanning exposure.

Claims (1)

[Claims] 1. A yellow image-forming, magenta image-forming, cyan image-forming and black image-forming silver halide emulsion comprising at least one layer each containing an internal latent image type silver halide grain on a support. In a direct positive silver halide color photographic light-sensitive material having a layer, the spectral sensitivity of the black image-forming silver halide emulsion layer is different from that of the yellow image-forming, magenta image-forming and cyan image-forming silver halide emulsion layers. A direct positive silver halide color having a common portion with the spectral sensitivity region and containing at least one nitrogen-containing heterocyclic compound having a mercapto group in the black image forming layer-forming silver halide emulsion layer. Photographic material.