JPH05134349A - Direct positive silver halide color photographic sensitive material and production of color proof - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material for color proofs at high production efficiency and to obtain a production method of color proofs using the same. CONSTITUTION:This direct positive silver halide color photographic sensitive material has picture image forming layers on a supporting body. These layers are at least one silver halide emulsion layer for each yellow, magenta and cyan picture images having different spectral sensitivity and containing silver halide particles to form internal latent images, and at least one black-color image forming layer containing silver halide particles to form internal latent images. The magenta picture image forming layer contains at least one kind of magenta picture image forming coupler and at least one kind of yellow picture image forming coupler. The black color picture image forming layer has a spectral sensitivity region including common regions with spectral sensitivity regions of the silver halide emulsion layers for formation of yellow, magenta, and cyan picture images. The color proof is produced with using this photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is preferably used for producing a proof color image (color proof) from a plurality of black and white halftone images obtained by color separation and halftone image conversion in a color plate making / printing process. And a method for producing a color proof using the same.

[0002]

BACKGROUND OF THE INVENTION There are primarily two types of techniques known in the art for obtaining direct positive images. One of the types is to use an emulsion containing silver halide grains having fog nuclei in advance and destroy the fog nuclei or latent image in the exposed area by utilizing the solarization or Herschel effect, etc. You get a positive directly. The other type uses an emulsion containing an internal latent image type silver halide grain that does not cause fog (generally surface fog) until the time of image exposure, and performs fog after image exposure (nucleation treatment).
Then, surface development is performed, or after image exposure, a positive image is directly obtained by performing surface development while performing fog treatment.

The above-mentioned fog treatment may be performed by exposing the whole surface, chemically using a fog agent, using a strong developing solution, or by heat treatment. The emulsion containing the internal latent image type silver halide emulsion grains is a silver halide which has a photosensitive nucleus mainly inside the silver halide crystal grains and forms a latent image inside the grains upon exposure. A grain-containing emulsion.

Of the above two techniques for forming a positive image, the latter type generally has higher sensitivity than the former type and is suitable for applications requiring high sensitivity.
Various techniques have been known so far in this technical field. For example, U.S. Patents 2,592,250 and 2,466,957
No. 2, No. 2,497,875, No. 2,588,982, No. 3,761,266,
No. 3,761,276, No. 3,796,577 and British Patent 1,151,363
There is a method described in the issue.

Although the mechanism of forming a positive image is not always clear, for example, Photographic Science and Engineering (Photographic Science and Engineering)
andEngineering) Vol. 20, p. 158 (1976), describes as follows.

Photoelectrons generated in the silver halide crystal grains by imagewise exposure are selectively trapped inside the grains to form an internal latent image. Since this internal latent image acts as an effective trap center for electrons in the conduction band, in the exposed particles, the electrons injected in the subsequent fog development process are trapped inside and assist the latent image. Become. In this case, the latent image is not developed by surface development because it is inside. On the other hand, in particles that have not been subjected to image exposure, at least some of the injected electrons are captured on the surface of the particle and a latent image is formed there, so that the particle is developed by surface development.

Although a positive image can be formed by using the above-mentioned known technique, further improvement of photographic performance is desired for practical application of these photographic light-sensitive materials to various photographic fields.

On the other hand, as a method for obtaining a color proof from a plurality of black and white halftone dot images obtained by color separation and halftone dot image conversion in the conventional color plate making / printing process, a photopolymer or a diazo compound is used. 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 simply by overlapping four color (subtractive primary colors and black) film sheets. There is a drawback in that gloss is generated by stacking, and therefore, a texture different from that of the printed matter is obtained.

In the surprint method, a colored image is superposed on one support, and a method of obtaining a colored image by toner development utilizing the adhesiveness of a photopolymerizable material is disclosed in US Pat. No. 3,582,327. Nos. 3,607,264 and 3,620,726.

Further, after transferring to a support using a photosensitive coloring sheet and forming an image by exposure and development, another coloring sheet is laminated thereon, and the same process is repeated to form a color proof. A method of doing this is known from Japanese Patent Publication No. 47-27441 and Japanese Patent Publication No. 56-501217.

Further, there is a method of forming a color image on a single support by transferring each color image obtained by exposing and developing the corresponding color separation film using a photosensitive color sheet.
-Known as No. 97140. 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 drawbacks that images must be superposed or transferred in the process of producing a color proof, which requires a long operation time and a high manufacturing cost.

As a solution to these drawbacks, a method for producing a color proof by using a silver salt color photographic light-sensitive material having a white support is disclosed in JP-A-56-113139 and JP-A-56-104335. 62-280746, 62-280747, 62-
280748, 62-280749, 62-280750, 62-28084
No. 9 etc.

In this method, a color-separated black-and-white halftone image composed of a plurality of sheets converted from a color original into a halftone image which has been color-separated is sequentially printed on one sheet of color paper by a method such as contact printing, and color development is performed. A color image formed by a dye formed from a coupler imagewise by color development is used as a proof image.

However, in this technique, when the color image is approximated to the printed matter, the density of the black image such as characters is insufficient as compared with the printed matter, and the density of the black image such as the characters is increased to approximate the density of the printed matter. If the measures are taken, there is a drawback that the degree of approximation of the color image of the printed matter deteriorates and it is difficult to satisfy both of them.

As a technique for improving this drawback, a technique of providing a fourth black plate layer having a spectral sensitivity different from that of any of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer is conventionally known. There is. For example, in JP-A-3-122637,
A technique using four types of image forming layers of yellow, magenta, cyan, and black is disclosed. Further, JP-A-2-289846,
No. 2-183251 and the like also disclose a technique for improving this problem, but in any case, it cannot be put to practical use such as increasing the number of exposures, impairing productivity, and lacking image stability. Further improvements are needed.

[0018]

OBJECTS OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide color photographic light-sensitive material (hereinafter also simply referred to as "light-sensitive material").
When producing a color proof from the halftone image information obtained by color separation and halftone image conversion using, a color proof with an improved degree of approximation to the image quality of the printed matter can be obtained with high production efficiency. It is to provide a proof light-sensitive material and a method for producing a color proof using the same.

[0019]

The above object of the present invention is achieved by the following configurations.

(1) On a support, at least one yellow image-forming silver halide emulsion layer containing internal latent image type silver halide grains having different spectral sensitivities, and at least one magenta image-forming halogenated silver halide layer. A direct positive silver halide color photographic light-sensitive material having a silver emulsion layer, at least one cyan image-forming silver halide emulsion layer and at least one black image-forming layer containing internal latent image type silver halide grains. At least 1 in the magenta image forming layer
One magenta image-forming coupler and at least one yellow image-forming coupler, and wherein the black image-forming layer is the yellow image-forming silver halide emulsion layer,
A direct positive silver halide color photographic light-sensitive material having a spectral sensitivity region common to the spectral sensitivity region of each of the magenta image forming silver halide emulsion layer and the cyan image forming silver halide emulsion layer.

(2) A yellow image forming layer and a magenta image forming layer are formed on a support based on halftone dot image information consisting of color-separated yellow image information, magenta image information, cyan image information and black image information. In the method for producing a color proof by exposing a direct positive silver halide color photographic light-sensitive material having a cyan image forming layer and a black image forming layer, the direct positive silver halide color photographic light-sensitive material is the direct light-sensitive material described in (1) above. A method for producing a color proof which is a positive silver halide color photographic light-sensitive material.

The present invention will be described in more detail below.

The non-pre-fogged internal latent image type silver halide grains according to the present invention mainly form a latent image inside the silver halide grains and have most of the photosensitive nuclei inside the grains. Grains including any silver halide.

Particularly preferably, the coated silver amount is about 1 to 3.5 g.
A portion of the sample coated on the transparent support so as to be in the range of 1 / m ² is exposed to the light intensity scale for a certain period of time from about 0.1 second to about 1 second, and is substantially halogenated. When only the surface image of a grain not containing a silver solvent is developed using the following surface developer A at 4 ° C. for 4 minutes, another part of the same emulsion sample is similarly exposed to expose the inside of the grain. It is an emulsion showing a maximum density which is not more than 1/5 of the maximum density obtained when the image is developed with the following internal developer B at 20 ° C. for 4 minutes. More preferably, the maximum density obtained with surface developer A is less than the maximum density obtained with internal developer B.
It is not larger than 1/10.

(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 to 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 is added to 1000 ml Also, the internal latent image type silver halide emulsion in the present invention can be prepared by various methods. Including those prepared in. 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. Patents 3,
No. 271,157, No. 3,447,927 and No. 3,53,291, emulsions having silver halide grains containing a polyvalent metal ion described therein, or silver halide grains containing a dopant described in U.S. Pat. A silver halide emulsion in which the grain surface is weakly chemically sensitized, or JP-A-50-8524 and 50-38525.
And the silver halide emulsions described in JP-A Nos. 53-2408 and 53-2408, and the silver halide emulsions 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 shape of particles is cubic, octahedral, (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 a polydisperse emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion 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 rm is the total weight of silver halide grains.
It means 60% or more, preferably 70% or more, and more preferably 80% or more. Here, the average particle size rm is
The product of the frequency ni and ri ^{3 of} particles having a particle size ri ni × ri ³
Is defined as the particle size ri when the maximum is (effective number 3
Digits and minimum digits are rounded to 4). In the case of spherical silver halide grains, the grain size means the diameter, or
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 can be obtained, for example, by magnifying the particles with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is not measured). 1000 against discrimination
There shall be more than one).

A particularly preferred highly monodisperse emulsion is one having a distribution width of 20% or less defined by (grain size standard deviation / average grain diameter) × 100 = distribution breadth (%). Here, the average particle size and the particle size standard deviation are obtained from ri defined above.

The monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to pAg and p in a gelatin solution containing seed grains.
It can be obtained by adding by the double jet method under the control of H 2. To determine the addition rate, refer to JP-A-54
-48521 and 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 with 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 sensitizing dyes, Research Disclosure (hereinafter abbreviated as RD) No. 15162 and
Reference can be made to No. 17643.

In the present invention, the yellow image forming layer, the magenta image forming layer and the cyan image forming layer have mutually different spectral sensitivities. This is at least 4 times higher than the spectral sensitivities of the other layers at any wavelength in the spectral sensitivity range of each layer.
It suffices that there be a wavelength exhibiting a double sensitivity, and preferably a wavelength exhibiting at least a 8 times sensitivity.

In the present invention, for the black image forming layer, any conventionally known method can be used as long as a black image is formed after development. For example, an image formed by leaving a silver image after development processing can be used, or a black coupler that forms a black image by color development can be used. Further, a black image can be obtained by mixing a yellow coupler, a magenta coupler and a cyan coupler.

In the present invention, the black image forming layer is common to the respective spectral sensitivity regions of the yellow image forming silver halide emulsion layer, the magenta image forming silver halide emulsion layer and the cyan image forming silver halide emulsion layer. It has a spectral sensitivity region having a portion. That is, the black image forming layer of the present invention has sensitivity to light having any wavelength in the spectral sensitivity wavelength range of the yellow image forming layer, and has any wavelength in the spectral sensitivity wavelength range of the magenta image forming layer. Of the cyan image forming layer, and also has sensitivity to light of any wavelength in the spectral sensitivity wavelength range of the cyan image forming layer.

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

The magenta image-forming layer of the present invention may be composed of a single silver halide emulsion layer or a plurality of silver halide emulsion layers having substantially the same spectral sensitivity. .. In the present invention, the magenta image forming layer contains at least one magenta image forming coupler and at least one yellow image forming coupler.

As the magenta dye-forming coupler used in the present invention, known 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers, acylacetonitrile type couplers, indazolone type couplers and the like can be used. However, a magenta coupler represented by the following general formula [MI] is particularly preferable.

[0039]

[Chemical 1]

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, and 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 formation Compound residues, bridged hydrocarbon compound residues and the like are also included.

The substituent represented by R, the group represented by X which can be removed by the reaction with the oxidation product of the color developing agent, 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. ..

Typical examples of the magenta coupler represented by the general formula [MI] are shown below.

[0044]

[Chemical 2]

[0045]

[Chemical 3]

[0046]

[Chemical 4]

[0047]

[Chemical 5]

[0048]

[Chemical 6]

As another specific example, European Published Patent 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), pp. 2047-2052, U.S. Patent 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.

In the present invention, as the yellow dye forming coupler contained in the magenta image forming layer, known acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Particularly preferred are couplers represented by the following general formula [Y-I]. Among the couplers represented by the general formula [Y-I], particularly preferred are couplers having a pKa value not lower than 3 by the pKa value of the magenta coupler to be combined.

[0053]

[Chemical 7]

In the formula, R ₁ represents a halogen atom or an alkoxy group, R ₂ represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent, and R ₃ represents a substituent. Represents an acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group or an aryloxy group. Z ₁ is a hydrogen atom,
It represents a monovalent organic group that can be released by a coupling reaction with a halogen atom or an oxidized product of a color developing agent.

Typical examples of the yellow coupler represented by the general formula [Y-I] include compounds Y-1 to Y-shown in the upper left column on page 13 to the lower left column on page 17 of JP-A-2-139542. 58.

The ratio of the contents of the magenta coupler and the yellow coupler in the magenta image forming layer of the light-sensitive material of the present invention depends on the printing ink whose magenta image forming layer has a spectral absorption of a dye image which is magenta. It may be determined so as to approximate the spectral absorption of the printed image. Specifically, the range of 0.02 to 0.5 mol of the yellow coupler is usually suitable for 1 mol of the magenta coupler. 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.

The fog treatment in the present invention can be carried out by exposing the entire surface or by using a compound which generates fog nuclei, 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 time of the whole surface exposure 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, if the exposure amount is excessively increased, 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. The fog agent only needs to be present at the time of development processing. For example, in the constituent layers other than the support of the light-sensitive material (in particular, among them). It is preferably contained 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. The preferable amount added is 1 to 1,500 mg, preferably 10 to 10 mg per mol of silver halide when added to the silver halide emulsion layer. 1,0
It is 00 mg. When it is added to a processing solution such as a developing solution, the preferable addition amount is 0.01 to 5 g / l, particularly preferably 0.05 to 1 g.
/ L.

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. In the present invention, both an adsorption type and 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- Hydrazine compounds such as methylsulfonyl-2-phenylhydrazine, 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine, 1-benzoyl-2-phenylhydrazine, 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-3-methylpyrido [2,1
-b] N-substituted quaternary cycloammonium salts such as benzothiazolium bromide; 5- (3-ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] Rhodanine, 1,3-bis [4- (2-formylhydrazino) phenyl] thiourea, 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3,4- Examples thereof include latrahydroacridinium trifluoromethanesulfonate and 1-formyl-2- [4- {3- (2-methoxyphenyl) ureido} phenyl] hydrazine.

The light-sensitive material having a silver halide emulsion layer according to the present invention is directly exposed to light after imagewise exposure or is subjected to development processing in the presence of a fogging agent to directly form a positive image.

As the developer that can be used in the developer used for developing the light-sensitive material according to the present invention, a conventional silver halide developer, for example, polyhydroxybenzenes such as hydroquinone, aminophenols and 3-pyrazolidone can be used. , Ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or a mixture thereof. 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. Can be mentioned. 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.

Known photographic additives can be used in the light-sensitive material of the present invention.

Known photographic additives include, for example, the compounds described in RD17643 and RD18716 shown in the table below.

Additive 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 contamination 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 to 27 XI 650 Right Plasticizer 27 XII 650 Right Sliding agent 〃 〃 Static inhibitor 〃 〃 Matting agent 28 XVI 650 Right binder 29 IX 651 Right In the emulsion layer of the light-sensitive material of the present invention, a color developing agent is used. A dye-forming coupler capable of forming a dye by a coupling reaction with an oxidant thereof 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.

It is desirable that these dye-forming couplers have a group having a carbon number of 8 or more, which is called a ballast group, which makes the coupler non-diffusible in the molecule. Also, these dye-forming couplers need only reduce 4 molecules of silver ions in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two 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 directly bound to the coupling position and an inhibitor bound to the coupling position via a divalent group, and are separated 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 developer but does not form a dye can be used in combination with the dye-forming coupler.

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.

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD17643, page 28 and RD18716.
Those described on page 647 can be mentioned. Suitable supports are polymer films, papers and the like, which may be treated for enhancing the adhesiveness, antistatic property and the like.

[0076]

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. An aqueous solution containing ammonia and silver nitrate was further added to the obtained core emulsion, and potassium bromide and sodium chloride (molar ratio KBr: NaCl = 4
An aqueous solution containing 0:60) 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 emulsion EM-1 was 8%.

(Preparation of Blue Sensitive Emulsion EM-B) After sensitizing EM-1 with sensitizing dye D-1, 600 mg of stabilizer T-1 was added per mol of silver to prepare blue sensitive emulsion EM-B. It was made.

(Preparation of Green Sensitive Emulsion EM-G) 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 to EM-1 for color sensitization.

(Preparation of red-sensitive emulsion EM-R) Red-sensitive emulsion EM-R was prepared in the same manner as blue-sensitive emulsion except that sensitizing dyes D-3 and D-4 were added to EM-1 for color sensitization. Was produced.

(Preparation of pan-sensitive emulsion EM-P) Same as the blue-sensitive emulsion except that sensitizing dyes D-1, D-2, D-3 and D-4 were added to EM-1 for color sensitization. And general emulsion EM-
P was prepared.

(Preparation of Infrared Sensitive Emulsion EM-I) EM-1
An infrared-sensitive emulsion EM-I was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dye D-5 was added thereto for color sensitization.

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

[0085]

[Chemical 8]

The above EM-B, EM-G, EM-R and EM
Using -P, the first to tenth layers were applied in the following constitution on the surface of the support laminated on both sides with polyethylene.
SA-1 and SA-2 were used as coating aids,
Samples 1 to 5 were prepared using H-1 as a hardener. The applied amount is shown in g / m ² .

Layer composition Coating amount 10th 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 9th 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 Solvent (SO-1) 0.615 Eighth layer Gelatin 0.75 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Seventh 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, ST-2, T-1) 6th layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS -1) 0.055 solvent (SO-2 0.072 5th 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 4th layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.14 (Green-sensitive layer) Green-sensitive emulsion EM-G (coated silver amount) 0.40 Magenta coupler (Table-A) Yellow coupler (Table-) A) Anti-staining agent (AS-2) 0.0152 Solvent (SO-1) 0.248 Inhibitor (ST-1, ST-2, T-1) Second layer Gelatin 0.75 (Intermediate layer) Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 First layer Gelatin 1.10 (Red-sensitive layer) Red-sensitive emulsion EM-R (Coating silver amount) 0.24 Cyan coupler (CC-1) 0.352 Solvent (SO-1) 0.248 Antistain agent (AS) -2) 0.012 inhibitor ( T-1, ST-2, T-1) in the same manner as Sample -1～5, the EM-B, EM-
Using G, EM-R and EM-I, a silver halide color photographic light-sensitive material sample-6 having the following constitution was prepared. The applied amount is shown in g / m ² .

Layer composition Coating amount 10th 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 9th layer Gelatin 1.14 (Blue-sensitive layer) Blue-sensitive emulsion EM-B (Amount of coated silver) 0.4 Yellow coupler (YC-1) 0.656 Anti-stain agent (AS-2) 0.02 Solvent (SO-1) 0.656 Inhibitor (ST-1, ST-2, 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 (YC layer) Yellow colloidal silver 0.1 Anti-color mixing agent ( AS-1) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 6th layer Gelatin 0.54 (Intermediate layer) Color mixture inhibitor (AS-1) 0.055 Solvent (SO-2) 0.072 5th layer Gelatin 1.14 ( Green-sensitive layer) Green-sensitive milk EM-G (Amount of coated silver) 0.40 Magenta coupler (Table-A) Yellow coupler (Table-A) Anti-stain agent (AS-2) 0.0152 Solvent (SO-1) 0.248 Inhibitor (ST-1, ST-2, 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 (amount of coated silver) 0.24 Cyan coupler (CC-1) 0.352 Solvent (SO-1) 0.248 Anti-staining agent (AS-2) 0.012 Inhibitor (ST-1, ST-2, T-1) Second layer Gelatin 0.75 (Intermediate layer) Mixed color Inhibitor (AS-1) 0.055 Solvent (SO-2) 0.072 First layer Gelatin 1.05 (Infrared photosensitive layer) Infrared photosensitive emulsion EM-I (Amount of coated silver) 0.30 Yellow coupler (YC-1) 0.21 Magenta coupler (MC-1) 0.063 Cyan coupler (CC-1) 0.110 Solvent (SO-1) 0.615 The additives used for sample preparation are as follows.

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-Hydroxy-4,6-dichloro-s-triazine / sodium AS-1: 2,5-di-t-octylhydroquinone AS-2: 2,5-di-t-butylhydroquinone SO- 1: Trioctyl phosphate SO-2: Dioctyl phthalate ST-1: 1- (3-acetamido) phenyl-5-mercaptotetrazole ST-2: N-benzyladenine

[0090]

[Chemical 9]

[0091]

[Chemical 10]

With respect to Samples 1 to 5 obtained as described above, halftone dots including a chart portion in which the halftone dot area was changed from 0 to 100% for each image of black, yellow, magenta, and cyan with 175 lines. The black original plate and the cyan original plate of the dot original document were brought into close contact with each other and exposed under the exposure condition-1 shown below. Next, the black plate and the magenta plate were brought into close contact with the sample and exposed under the exposure condition-2 shown below. Further, the black plate and the yellow plate were brought into close contact with the sample and exposed under the exposure condition-3 shown below.

Next, with respect to the prepared sample-6, sample-1
5 to 5, exposure was sequentially performed under exposure conditions 1 to 3, and only the black plate of the original document was brought into close contact with it and exposed under exposure condition 4 shown below.

The exposed light-sensitive material thus obtained was processed by the development processing steps shown below, and the (blue light density / green light density) ratio of the 100% halftone dot image of the obtained black image area was obtained. Table B shows the results of the ratio of the (blue light density / green light density) ratio of the 10% halftone dot image to.

(Exposure condition-1) Each of the light-sensitive materials was passed through a red filter (Ratten No. 26) and an ND filter, and when the white light was exposed, the density of the ND filter was adjusted so that the red light density after the development processing was as follows. With minimum exposure
Expose for 0.5 seconds.

(Exposure condition-2) Each of the light-sensitive materials was passed through a green filter (Ratten No. 58) and an ND filter, and when the white light was exposed, the ND filter density was adjusted so that the green light density after the following development processing was With minimum exposure
Expose for 0.5 seconds.

(Exposure condition-3) Each of the light-sensitive materials was passed through a blue filter (Ratten No. 47B) and an ND filter, and when the white light was exposed, the density of the ND filter was adjusted so that the green light density after the following development processing was Expose for a minimum of 0.5 seconds with the minimum exposure.

(Exposure condition-4) The ND filter density was adjusted when the tungsten light was exposed through the infrared filter and the ND filter to the samples sequentially exposed with the respective light-sensitive materials under the above exposure conditions-1 to 3 Then, it is exposed for 0.5 seconds with the minimum exposure amount that minimizes the visible light density after the development processing described below. Exposure condition only through the infrared filter-
Set to 4. A daylight fluorescent lamp was used as a light source under exposure conditions-1 to 3.

Processing was carried out according to the following processing steps to obtain a photographic image. However, the fog exposure was carried out with the surface of the photosensitive material 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 ° C 40 seconds Treatment liquid composition is as follows.

(Color developer) 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 pentaacetic acid Sodium 2.0g 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
Adjust the pH to 10.15 by adding 15.0 ml water to make the total volume 1000 ml.

(Bleach-fixing solution) Diethylenetriamine 5 ferric ammonium acetate 90.0 g Diethylenetriamine 5 acetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1,2,4- Triazole 0.15g Adjust pH to 7.1 with potassium carbonate or glacial acetic acid, add water to make 1000ml.

(Stabilizing Solution) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to make 1000 ml, and add ammonium hydroxide or Adjust the pH to 7.5 with sulfuric acid.

The stabilization treatment was a countercurrent system having a two tank structure.

Table-A Sample No. Magenta coupler Yellow coupler Coated amount (mole / m ² ) Coated amount (mole / m ² ) 1 (Comparative) MC-1 (4.4 × 10 ⁻⁴ ) None 2 ( ^Pieces ) Invention) MC-1 (〃) YC-1 (1.0 × 10 ^-4 ) 3 (Invention) MC-2 (〃) YC-1 (〃) 4 (Invention) MC-2 (〃) YC-2 ( 〃) 5 (invention) MC-3 (〃) YC-3 (〃) 6 (comparison) MC-1 (〃) YC-1 (〃) table -B sample _{No. (D B / D G)} 10 % (D _B / D _G ) 100% Black image part Magenta image part 1 (Comparison) 1.16 0.88 2 (present invention) 1.05 0.98 3 (present invention) 1.02 1.03 4 (present invention) 0.97 0.94 5 (present invention) 0.99 1.04 6 (Comparison) 0.92 1.07 The value in Table-B above is an index that represents the variation in color tone between the large and small points, and approaches 1.0 when the variation is small. As is clear from Table-B, the sample of the present invention has a large halftone dot and a small halftone dot (blue light density / green light density = DB / _{B) in} both the black image portion and the magenta image portion.
The D _G ) ratio was almost constant, the evaluation value was close to 1.0, the color tone was stable, and a favorable image could be obtained by three times of exposure.

Further, although the color tone variation of sample-6 is relatively small, the exposure is required four times, so that the work is complicated and the efficiency in producing a large number of proofs is remarkably inferior. It was found that the performance was not stable due to large variations in the image density when the sample of the content was prepared.

Example 2 (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. The breadth of distribution of emulsion EM-2 was 12%.

(Preparation of Blue Sensitive Emulsion EM-2B) EM-2
Was sensitized with sensitizing dye D-1 and then T-1 was added per mol of silver.
600 mg was added, and further FA-1 and FA-2 were added in an amount of 5 × 10 ^-4 mol and 8 × 10 ^-5 mol, respectively, per mol of silver to prepare a blue-sensitive emulsion EM-2B.

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

(Preparation of Red Sensitive Emulsion EM-2R) EM-2
In addition to sensitizing dyes D-3 and D-4 to sensitize
A red-sensitive emulsion EM-2R was prepared in the same manner as the green-sensitive emulsion.

(Preparation of pan-sensitive emulsion EM-2P) EM-2
A general-purpose emulsion EM was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dyes D-1, D-2, D-3 and D-4 were added to the emulsion.
-2P was prepared.

[0112]

[Chemical 11]

(Preparation of Sample-7) Sample of Example 1-
Sample-7 was prepared in the same manner as in 2. However, Example 1
Instead of EM-B, EM-G, EM-R, EM-P,
EM-2B, EM-2G, EM-2R, EM-2
A color light-sensitive material sample-7 was prepared in the same manner as sample-2 except that P was used.

The obtained sample was exposed in the same manner as the sample-2 of Example 1, and then processed according to the following process step-2.

(Processing Step-2) Temperature Time Image 37 ° C. 130 seconds Bleaching fixing 35 ° C. 45 seconds Stabilization treatment 25-30 ° C. 90 seconds Drying 60-85 ° C. 40 seconds Developer and bleach-fixing solution used here The formulation of each processing solution of the stabilizing solution is exactly the same as that used in Example 1.
The stabilization treatment was a countercurrent system with a two tank structure.

The image obtained by three times of exposure had the same good color tone as the sample of the present invention of Example 1.

[0117]

By using the direct positive silver halide color photographic light-sensitive material of the present invention, there is little variation in the color tone between the large dots and the small dots of the halftone dot, and the color of which the approximation of the image quality to the printed matter is improved. The proof could be obtained with 3 exposures.

Claims (2)

[Claims] 1. At least one yellow image-forming silver halide emulsion layer having internal latent image type silver halide grains and having different spectral sensitivities, and at least one magenta image-forming silver halide on a support. Emulsion layer, at least 1
A direct positive silver halide color photographic light-sensitive material having one layer of a cyan image-forming silver halide emulsion layer and at least one black image-forming layer containing internal latent image type silver halide grains, wherein the magenta image-forming layer comprises At least one magenta image-forming coupler and at least one yellow image-forming coupler, and the black image-forming layer comprises the yellow image-forming silver halide emulsion layer, the magenta image-forming silver halide emulsion layer, and A direct positive silver halide color photographic light-sensitive material having a spectral sensitivity region having a common part with the spectral sensitivity region of each of the cyan image forming silver halide emulsion layers. 2. A yellow image forming layer, a magenta image forming layer, and cyan on a support based on halftone dot image information consisting of color-separated yellow image information, magenta image information, cyan image information, and black image information. A method for producing a color proof by exposing a direct positive silver halide color photographic light-sensitive material having an image forming layer and a black image forming layer, wherein the direct positive silver halide color photographic light-sensitive material is a direct positive silver halide color photographic light-sensitive material. A method for producing a color proof, which is a silver halide color photographic light-sensitive material.