JP2003207874A - Silver halide color photographic sensitive material and color image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in stability with respect to a change of exposure time, temperature and humidity changes in exposure and shortening of processing time and having excellent color developing properties and high image quality, and to provide a color image forming method using the same. <P>SOLUTION: In the silver halide color photographic sensitive material having on a support a photosensitive silver halide-containing yellow image forming layer, a photosensitive silver halide-containing magenta image forming layer and a photosensitive silver halide-containing cyan image forming layer, the difference ΔLogE between light exposure (LogEd) giving the maximum point γ(γmd) of each color image obtained by development after exposure for 10<SP>-6</SP>sec per pixel and light exposure (LogEa) giving the maximum point γ (γma) of each color image obtained by development after exposure for 0.5 sec per pixel is ≤0.1. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides high-quality prints of both character images and scene images regardless of the model of the digital exposure machine, and is stable against variations in development processing conditions and exposure conditions. The present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a high image and a color image forming method.

[0002]

2. Description of the Related Art In recent years, the opportunities for handling images as digital data have been rapidly increasing due to improvements in computer computing power and advances in network technology. Image information converted into digital data by using a scanner or the like can be relatively easily edited and processed on a computer, and further, data such as characters and illustrations can be added.
As a hard copy material for creating a hard copy based on such digitized image information, for example,
Examples include sublimation type thermal transfer prints, fusion type thermal transfer prints, inkjet prints, electrostatic transfer type prints, thermo-autochrome prints, and silver halide photographic light-sensitive materials. Among them, silver halide color photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials (Also referred to as) is highly sensitive compared to other print materials, such as high sensitivity, excellent gradation, and excellent image storability. It is widely used today for making high quality hard copies.

Image information converted into digital data using a scanner or the like is edited and processed on a computer,
Furthermore, since it is relatively easy to add data such as characters and illustrations, for example, images based on photographed data of people, landscapes, still life, etc. (hereinafter referred to as “scene image”).
And character images (especially thin and small black character images)
Opportunities to handle mixed images are increasing. for that reason,
In image output based on digital data, it is necessary to simultaneously satisfy the two requirements of reproducing a scene image more naturally and a character image without blurring.

Also, digital still cameras of the last few years,
Alternatively, an image input device such as a film scanner is remarkably increased in resolution, and in order to output an image utilizing the high quality image data, an increase in resolution of an output device (digital exposure device) is also under study. Recently, various digital exposure machines have been commercialized, but many models are now on sale as digital image exposure apparatuses that perform such exposure, and in combination with the progress of exposure light sources and control devices, new Many digital image exposure devices have also been developed. Among these digital image exposure devices, as an exposure light source,
Devices using a sharp light source wavelength distribution such as lasers and LEDs are becoming mainstream.

However, although various types of image devices have been released by various companies due to the widespread use of various digital image exposure devices, the types of lasers and LEDs mounted on them are not uniform, and exposure is performed for each exposure device. The wavelength and the exposure time are also different, so the digital exposure time is significantly different from the conventional negative exposure analog exposure, and the exposure time is 10,000 to 100,000 times the exposure time from 10 ^-7 seconds to 10 ^-2 seconds. Due to the difference in the exposure time, the tolerance for the exposure time has been strongly demanded. Furthermore, due to the nature of the equipment, the digital exposure device is easily affected by heat, and therefore the durability against temperature and humidity during exposure has become stronger than that required for image formation by a conventional analog exposure device. . Also, with the spread of minilabs, some photo shops offer a service that the time from receiving an order from a customer to finishing the print is short, within 35 minutes, as a service. There is a strong demand from the market for demands and to provide beautiful images, especially in digital, even if the processing time is short.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide color photographic light-sensitive material and a color image forming method thereof, which can always obtain a high quality digital image even when the exposure time is largely changed. To do. A second object of the present invention is to provide a silver halide color photographic light-sensitive material and a color image forming method thereof which can always obtain a high image stably against environmental changes such as temperature and humidity during exposure. A third object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining a high image without changing the image even if the processing time is shortened and a color image forming method thereof. A fourth object is to provide a silver halide color photographic light-sensitive material excellent in color forming property and a color image forming method thereof.

[0007]

The above object of the present invention has been achieved by the following constitution.

1. On the support, a yellow image forming layer containing a photosensitive silver halide, a magenta image forming layer,
In a silver halide color photographic light-sensitive material having at least one cyan image forming layer, each pixel has 10
-Exposure time after exposure for ⁶ seconds, development process, exposure amount (LogEd) giving maximum point γ (γmd) of each color image obtained, and exposure time per pixel for 0.5 second After that, development processing is carried out, and the difference ΔLogE (LogEd-LogEa) with the exposure amount (LogEa) giving the maximum point γ (γma) of each color image obtained is 0.1 or less. Silver halide color photographic light-sensitive material.

2. On the support, a yellow image forming layer containing a photosensitive silver halide, a magenta image forming layer,
In a silver halide color photographic light-sensitive material having at least one cyan image forming layer, each pixel has 10
The effective gradation area (VE) of the color image obtained by developing after exposure for an exposure time of ^-10 seconds or more and 10 ^-3 seconds or less is 0.65 or more and 0.84 or less in each color image forming layer. 2. The silver halide color photographic light-sensitive material as described in 1 above, wherein

3. 3. The item 1 or 2, wherein at least one of the yellow image forming layer, the magenta image forming layer, and the cyan image forming layer contains a compound represented by the general formula (1). Silver halide color photographic light-sensitive material.

4. 4. A color image forming method, which comprises subjecting the silver halide color photographic light-sensitive material of any one of items 1 to 3 to development processing in a color development step of 25 seconds or less.

5. 4. A color image forming method, wherein the image formed on the silver halide color photographic light-sensitive material according to any one of items 1 to 3 has a scene image and a character image in the same image.

The details of the present invention will be described below. In the invention according to claim 1, the exposure amount (LogE) that gives the maximum point γ (γmd) of each color image obtained by performing development processing after exposure with an exposure time of 10 ⁻⁶ seconds per pixel
d) and the exposure amount (LogEa) that gives the maximum point γ (γma) of each color image obtained by performing development processing after exposure with an exposure time of 0.5 second per pixel ΔL
The feature is that ogE (LogEd-LogEa) is 0.1 or less.

First, the exposure amount difference ΔLogE that gives the maximum point γ of the image forming layers of each color will be described.

The term ΔLogE as used in the present invention means that each dye-forming layer is exposed for 10 ⁻⁶ seconds and 0.5 seconds and then developed, and each characteristic curve at a density of 0.8 is obtained. When they are superposed, the difference between the positions of the exposure amounts of the maximum points γ (Δ
It shows that LogE) is 0.1 or less.

In the present invention, "point γ" means T.
H. James edition "The Theory of th
e Photographic Process "4th
As described on page 502, edition γ = dD / dLogE (D represents density, E represents exposure amount), and a characteristic curve (D- It represents a differential value of an arbitrary point on LogE curve), and the maximum point γ indicates a point at which the point γ becomes a maximum.

The present inventors have found that ΔLogE in the case where characteristic curves are superposed at a density point of 0.8 is important for specifically forming a character image and a scene image beautifully, and this ΔLogE is When the exposure time is 0.1 or less, an image having good character quality and reproducibility of each scene image can be obtained even when the exposure time is 10 ^-6 seconds or 0.5 seconds, and when the exposure time is 0.07 or less, character bleeding occurs. It was found that an image with no image can be obtained.

In the invention according to claim 2, 1 per pixel
After exposure for an exposure time of 0 ^-10 seconds to 10 ^-3 seconds, the effective gradation area (VE) of the color image obtained by development processing is
The feature of each color image forming layer is 0.65 or more and 0.84 or less.

The effective gradation area (VE) referred to in the present invention is
It means a region where the density changes with the change of the exposure amount. Specifically, it shows a region where the value of the point γ is larger than 1.0, and VE in the present invention is 0.65 or more and 0.84 or less in each color image forming layer, and more preferably 0.65. It is above 0.80.

In the present invention, the effects of the present invention can be obtained by satisfying the requirements specified in the present invention in the exposure condition range in which the exposure time per pixel is 10 ^-10 seconds or more and 10 ^-3 seconds or less. However, in order to further clarify the effect of the present invention, the following evaluation method can be preferably used.

That is, a 1 cm square patch is exposed on the photosensitive material while changing the exposure amount by using a laser scanning exposure device adjusted so that the overlap between the rasters of the light beams is within the range of 5 to 30%. Then, using the following color developer (CDC-1), color development is carried out at 37 ± 0.5 ° C. for 45 seconds (after the color development, usual bleach-fixing and washing or stabilizing treatment is carried out). The reflection density of the gray patch portion of the obtained sample was measured, and a characteristic curve composed of the horizontal axis: exposure amount (LogE) and the vertical axis: reflection density (D) was created, and the exposure amount was increased for each step. The point gamma can be obtained by calculating the differential value of the density with respect to.
In the present invention, the time from the end of exposure to the start of development is 1 hour.

[Color developer (CDC-1)] Pure water 800 ml Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.02 g Potassium chloride 4.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfate 4.0 g N, N-diethylhydroxylamine 5.6 g triethanolamine 10.0 g diethylenetriaminepentaacetic acid sodium salt 2.0 g potassium carbonate 30 g Water was added to bring the total volume to 1 liter. The pH is adjusted to 10.1 with sulfuric acid or potassium hydroxide.

In the present invention, the diameter of the light beam (beam diameter) is the width of the raster. The light beam diameter mentioned here is the diameter of the light beam when the light beam intensity becomes e ^−2, and can be obtained, for example, by a beam monitor or the like in which a slit and a power meter are combined.

In the present invention, after exposure so that the exposure time per pixel is 10 ^-10 seconds or more and 10 ^-3 seconds or less,
The difference (ΔVE) between the VE value of the color image forming layer that maximizes the effective gradation area (VE) and the minimum VE value of the color image forming layer when color development processing is performed is 0.08 or less. Is preferred. When the value of ΔVE is small, the balance between the yellow, magenta, and cyan color images is maintained relatively well, and in particular, the color blurring of the character outline and the exposure scanning stripes in the solid image portion are reduced, which is preferable.

In the invention of claim 3, at least one of the yellow image forming layer, the magenta image forming layer and the cyan image forming layer contains the compound represented by the general formula (1). It is a feature.

The compound represented by the general formula (1) according to the present invention is a compound which functions as a high boiling point solvent for a coupler, and is a compound which is usually a liquid at room temperature and has a boiling point of 150 ° C. or higher.

In the general formula (1), R _{1 to} R ₃ each represent a substituent. Particularly preferable examples of R _{1 to} R ₃ include an alkyl group and an aryl group. Also,
It is preferable that LogP, which is a general physical property value, is 6.0 or more, and the relative dielectric constant is 6.0 or more.

LogP in the present invention is the logarithm of the partition coefficient P to n-octanol / water, and P = (solute concentration in n-octanol phase) / (solute concentration in water phase).

The value of LogP has been conventionally used as a measure of hydrophobicity. For example, the chemical review (Che
medical Review) 555, 71 (6), (19
71), SolubilityBehavior of
Organic Compound (Techniq
ue of Chemistry, vol21) (Jo
Published by hn Wiley, 1990), Chemosp
here, 1837, 18 (1989), Substi
tuent Constants For Corer
ation Analysis in Chemist
ry and Biology (John Wily & S
ons company, 1979) and the like.

Specific compounds represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0031]

[Chemical 2]

In the invention according to claim 4, the silver halide color photographic light-sensitive material has a processing time of 2 in the color development step.
A characteristic is that the development processing is performed in 5 seconds or less, and more preferably within 20 seconds.

As means for shortening the processing time of the color developing step, for example, the pH of the color developing processing solution is set to 10.30 or higher, more preferably 10.50 or higher, or the temperature of the color developing processing solution is set. The temperature may be 38 ° C. or higher, more preferably 40 ° C. or higher.

The composition of the silver halide emulsion used in the light-sensitive material of the present invention may be any halogen such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. Although it may have a composition, among them, silver chlorobromide or silver chloroiodide containing 95 mol% or more of silver chloride is preferable because the effect of the present invention is remarkable. From the viewpoint of rapid processability and process stability, a silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

In the light-sensitive material of the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide is also used from the viewpoint of reducing the softening of the characteristic curve in the high concentration region in high-intensity short-time exposure. It can be preferably used. In this case, the portion containing silver bromide in a high concentration may be an epitaxy-bonded silver halide grain, a so-called core-shell emulsion, or may not form a complete layer and may be partially There may only be regions of different composition.
The composition may change continuously or discontinuously. The portion where silver bromide is present at a high concentration is particularly preferably the surface of the silver halide grain or the apex of the crystal grain.

In the light-sensitive material of the present invention, it is preferable to use silver halide grains containing heavy metal ions from the viewpoint of reducing softening caused by high-intensity short-time scanning exposure. Examples of heavy metal ions that can be used for such purposes include, for example, Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and cadmium, zinc, mercury, and the like. Examples include Group 12 transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable.
These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the heavy metal ion forms a complex, examples of its ligand or ion include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitric acid. Ions, carbonyl, ammonia and the like can be mentioned.
Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to allow the above-mentioned heavy metal ions to be contained in the silver halide grains, the heavy metal compound is physically aged before the formation of silver halide grains, during the formation of silver halide grains, after the formation of silver halide grains and the like. It may be added at any time in each of the steps. In addition, in the addition, the solution of the heavy metal compound can be continuously carried out over the whole or part of the particle forming step.

When the above heavy metal ions are added to the silver halide emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
More preferably, it is 1 mole or more and 1 × 10 ^-2 mole or less, and particularly 1
× 10 ^-8 mol to 5 × 10 ^-5 mol or less.

In the light-sensitive material of the present invention, any shape of silver halide grains can be used. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. No. 4,183,756,
No. 4,225,666, JP-A-55-26589.
Issue, Japanese Examined Patent Publication No. 55-42737, and The Journal of Photographic Science (J. Photo.
gr. Sci. ) 21, 39 (1973) and the like, and the like, particles having a shape such as an octahedron, a tetradecahedron and a dodecahedron can be prepared and used. Further, grains having twin planes may be used.

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

The grain size of the silver halide grains according to the present invention is
There is no particular limitation, but in view of rapid processability, sensitivity and other photographic performance, preferably 0.1 to 1.2 μm,
More preferably, it is in the range of 0.2 to 1.0 μm. This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be expressed as diameter or projected area.

The grain size distribution of silver halide grains used in the light-sensitive material of the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably. Is to add two or more kinds of monodisperse emulsions having a coefficient of variation of 0.15 or less to the same layer. The coefficient of variation referred to here is a coefficient representing the breadth of the particle size distribution and is defined by the following formula.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Also, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used. The silver halide emulsion used in the light-sensitive material of the present invention may be one obtained by any of the acidic method, the neutral method and the ammonia method. The silver halide grains may be grown at one time or may be grown after preparing seed grains. The method for preparing the seed particles and the method for growing the particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof. Those listed are preferred. Further, as one form of the simultaneous mixing method, Japanese Patent Laid-Open No. 48521/54
It is also possible to use the pAg controlled de double jet method described in the publication.

Further, JP-A-57-92523 and 57-57
-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, water-soluble as described in German Published Patent No. 2,921,164, etc. Device for continuously changing the concentration of silver salt and water-soluble halide salt aqueous solution and adding the solution, Japanese Patent Publication No. 56
An apparatus for forming grains while keeping the distance between silver halide grains constant by taking out the reaction mother liquor from the reactor described in No. -501776 and concentrating it by ultrafiltration may be used. Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the light-sensitive material of the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion,
For example, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur. The amount of the sulfur sensitizer added is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect.
Approximately 5 × 10 ^{-10 to} 5 × 10 per mol of silver halide
^-5 mol, preferably 5 x 10 ^{-8 to} 3 x 10 ^-5 mol.

As the gold sensitizer, for example, various gold complexes other than chloroauric acid, gold sulfide and the like can be added.
Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. Is preferred. More preferably 1 × 10 ⁻⁵ or more
It is 1 × 10 ⁻⁸ mol. A reduction sensitization method may be used as the chemical sensitization method for the silver halide emulsion according to the present invention.

The silver halide emulsion used in the light-sensitive material of the present invention is for the purpose of preventing fog occurring during the process of preparing the light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Well-known antifoggants and stabilizers can be used. As an example of a preferable compound that can be used for such a purpose, Japanese Patent Laid-Open No. 2-1460
The general formula (I
The compound represented by I) can be mentioned, and more preferable specific compounds include (IIa-1) to (IIa-8) and (IIb-1) to (IIb) described on page 8 of the publication.
-7) compound or 1- (3-methoxyphenyl) -5
Examples thereof include compounds such as -mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds, depending on their purpose,
It is added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step, and the step of preparing a coating solution. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 to 1 mol per mol of silver halide
An amount of about 1 × 10 ⁻² mol is preferable, and 1 × 10 ^{−5 to} 5 ×
More preferably, it is 10 ⁻³ mol. In the coating liquid preparation process,
When it is added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ^-6 to 1 × 10 ^-1 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. preferable. When it is added to the constituent layers other than the silver halide emulsion layer, the amount in the coating film is 1 × 10 ⁻⁹ to 1 × 1 per 1 m ^2.
The amount is preferably about 0 ^-3 mol.

Dyes having absorption in various wavelength ranges can be used in the light-sensitive material of the present invention for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. Particularly, as a dye having absorption in the visible region, JP-A-3-251840 can be used.
The dyes of AI-1 to 11 described in JP-A No. 308, the dye described in JP-A-6-3770, and the dye described in JP-A-11-119379 are preferably used for infrared absorption. As the dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A No. 1-280750 have preferable spectral characteristics and a silver halide photographic emulsion. Is also preferable because it does not affect the photographic characteristics of the above and there is no stain due to residual color.

The amount of these dyes to be added is such that the exposure is carried out in an ultra-high illuminance and an extremely short time, such as the exposure by laser light,
In order to improve the sharpness in both exposure with high illuminance and short time such as exposure using an LED, the addition amount and the type of dye are appropriately selected so that the silver halide color photographic light-sensitive material has a thickness of 630 nm to 730 nm. 7. It has one spectral sensitivity maximum and the reflected light quantity at 670 nm is the incident light quantity.
It is preferable that the aspect ratio is 3% or more and 10% or less, one spectral sensitivity maximum is at 520 nm to 570 nm, and the reflected light amount at 550 nm is 38% of the incident light amount.
% Or more and 50% or less, and further has one spectral sensitivity maximum at 450 nm to 500 nm, and the reflected light amount at 460 nm is 50% of the incident light amount.
The embodiment in which the amount is from 63% to 63% is preferably used.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention because the white background can be improved. Examples of the compounds preferably used include the compounds represented by the general formula II described in JP-A-2-232652.

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

As the spectral sensitizing dye used for the spectral sensitization of the silver halide emulsion used in the light-sensitive material of the present invention, any known compound can be used. BS-1 to BS-8 described in page 28 of Kaihei 3-251840 can be preferably used alone or in combination. As the green-sensitizing sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. Also,
When image exposure is performed by infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye, and as the infrared-sensitive sensitizing dye, JP-A-4-285 is known.
The dyes of IRS-1 to 11 described in JP-A 950, pages 6 to 8 are preferably used. Also, these infrared, red,
For green and blue photosensitive sensitizing dyes, the supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and the supersensitizers described in JP-A-5-66515, pages 15 to 17 are described. It is preferable to use the compounds S-1 to S-17 in combination. The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

As a method for adding the sensitizing dye, the sensitizing dye may be dissolved in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and added as a solution, or as a solid dispersion. You may add.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized product of a color developing agent. Can also be used, but as a typical example, the wavelength range 3
Known as a yellow dye forming coupler having a spectral absorption maximum wavelength in 50 to 500 nm, a magenta dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a cyan dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm. The ones that are listed are typical.

A cyan coupler which can be preferably used in the light-sensitive material of the present invention is described in JP-A-4-11415.
The general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds include those described as CC-1 to CC-9 in the lower right column of page 5 to the lower left column of page 6 of the specification.

As a magenta coupler which can be preferably used in the light-sensitive material of the present invention, JP-A-4-1141 is known.
The general formula (M-
Examples thereof include couplers represented by I) and (M-II). Specific compounds include those described as MC-1 to MC-11 in the same publication, page 4, lower left column to page 5, upper right column. Among the above-mentioned magenta couplers, more preferred are couplers represented by the general formula (M-I) described in the right upper column of page 4 of the same publication, and among them, RM of the above-mentioned general formula (M-I). A coupler in which is a tertiary alkyl group is particularly preferable because it has excellent light resistance.
MC-8 described in the upper column on page 5 of the publication
MC-11 is preferable because it is excellent in color reproduction from blue to purple and red and is excellent in detail depiction ability.

A yellow coupler which can be preferably used in the light-sensitive material of the present invention is described in JP-A-4-1141.
The general formula (Y-
The couplers represented by I) can be mentioned. Specific compounds are described in YC- in the lower left column on page 3 of the specification.
1 to YC-9 can be mentioned. Above all, RY of the general formula [Y-1] in the specification of the publication.
A coupler in which 1 is an alkoxy group or JP-A-6-67
The coupler represented by the general formula [I] described in the specification of Japanese Patent No. 388 is preferable because it can reproduce a preferable yellow tone. Of these, examples of particularly preferable compounds are JP-A-4-11415.
YC-described in the lower left column of page 4 of Japanese Patent Publication No. 4
8, YC-9, and compounds represented by Nos. (1) to (47) described on pages 13 to 14 of JP-A-6-67388. The most preferable compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and page 11, page 17 to page 17.

When the oil-in-water type emulsion dispersion method is used as a method of adding the coupler or other organic compound used in the light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. Low boiling point and / or as required
Alternatively, a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added.
The high-boiling organic solvent that can be used to dissolve and disperse the coupler is represented by the general formula (1) according to claim 3.
Other than the compound represented by, for example, dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, phosphoric acid esters such as trioctyl phthalate, alcohols such as fatty acid alcohol are preferably used. To be Also,
The high-boiling point organic solvent preferably has a dielectric constant of 3.5 to 7.0. It is also possible to use two or more high boiling point organic solvents in combination.

Further, instead of the method using a high-boiling point organic solvent or in combination with a high-boiling point organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and the resulting mixture is emulsified by various dispersing means using a surfactant.
Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

The above-mentioned dispersion liquid is usually added to a coating liquid containing a silver halide emulsion, and the time from dispersion to addition to the coating liquid and the time from addition to the coating liquid to coating. Is preferably shorter, preferably within 10 hours, more preferably within 3 hours, and further preferably 2 hours.
This is a mode in which the time is within 0 minutes.

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specifically, A described in Japanese Patent Application Laid-Open No. 64-26854
-1-A-11 are mentioned. Further, a surfactant having a fluorine atom substituted in the alkyl group can also be used.

An anti-fading agent is preferably used in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, and general formula IIIB described in JP-A-3-174150.
A phenolic compound represented by JP-A-64-9044
No. 5, an amine compound represented by the general formula A, and general formulas XII and XII described in JP-A-62-182741.
The metal complexes represented by I, XIV and XV are particularly preferable for the magenta dye. Further, the compound represented by the general formula I ′ described in JP-A-1-196049 and JP-A-5-114
The compounds represented by the general formula II described in JP-A No. 17 are particularly preferable for yellow and cyan dyes.

The compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound described in JP-A-4-114154, page 10, lower left column, for the purpose of shifting the absorption wavelength of the coloring dye. Compounds such as (A'-1) can be used. In addition to this, US Pat.
The fluorescent dye-releasing compounds described in Japanese Patent No. 774,187 can also be used.

In the light-sensitive material of the present invention, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or is added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. A particularly preferable compound is the compound represented by the general formula II described in JP-A-4-133056, and the specifications of the same publications 13 to 1
Compounds II-1 to II-14 described on page 4 and compound 1 described on page 17 can be mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog and improve the light resistance of the dye image. Examples of preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are compounds represented by the general formula III-3 described in JP-A-1-250944, JP-A-SHO-6.
Compounds represented by the general formula III described in JP-A-4-66646 and UV-1L described in JP-A-63-187240.
To UV-27L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative. Also, hydrophilic colloids such as synthetic hydrophilic polymer substances such as single or copolymers can be used.

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination, for example, JP-A-61-249054 and 61-245153. It is preferable to use the compounds described in the publication. Further, in order to prevent the growth of molds and bacteria that adversely affect photographic performance and image storability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer. Further, in order to improve the surface properties of the light-sensitive material before or after processing, a slip agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 may be added to the protective layer. preferable.

Any material can be used as the support for the light-sensitive material of the present invention. Paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white Polypropylene, which may contain a pigment, polyethylene terephthalate support, baryta paper and the like can be used. Of these, a support having a waterproof resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, hydrated alumina, Examples thereof include titanium oxide, zinc oxide, talc and clay. Among the white pigments, barium sulfate and titanium oxide are preferable.

The amount of the white pigment contained in the water resistant resin layer on the surface of the support is 13% by mass in order to improve the sharpness.
The above is preferable, and further 15% by mass is preferable.

In the paper support used for the light-sensitive material of the present invention, the degree of dispersion of the white pigment in the water resistant resin layer is as described in JP-A-2-
It can be measured by the method described in Japanese Patent No. 28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

The center surface average roughness (SRa) of the support
Is more preferably 0.15 μm or less, further preferably 0.12 μm or less, because the effect of good gloss is obtained. Further, in the water-resistant resin containing a white pigment of the reflective support or in the applied hydrophilic colloid layer, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after the treatment, for example, ultramarine blue, It is preferable to add a slight amount of a blue tinting agent, a red tinting agent, or an optical brightening agent such as an oil-soluble dye.

In the light-sensitive material of the present invention, the surface of the support is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then each photographic constituent layer is directly or undercoated (adhesiveness of the surface of the support, Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The present invention is preferably applied to a light-sensitive material which forms an image for direct viewing. Examples thereof include color papers, color reversal papers, photosensitive materials for forming positive images, photosensitive materials for displays, and photosensitive materials for color proofs.

In the color image forming method of the present invention, known compounds can be used as the aromatic primary amine developing agent used in the developing treatment. Examples of these compounds include N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-
Amino-5- (N-ethyl-N-laurylamino) toluene, 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline, 2-methyl-4- (N-ethyl-N- (β -Hydroxyethyl) amino) aniline, 4
-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p -Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline, 4-amino-3- Methyl-N-ethyl-N- (γ-hydroxypropyl) aniline and the like can be mentioned. In addition to the aromatic primary amine color developing agents, for example, European Patent 565,1
No. 65, No. 572, 054, No. 593, 110.
No. 8-202002 and 8-227131.
No. 8-243390, Japanese Patent Application No. 10-171335.
No. sulfonylhydrazide and carbonylhydrazide type color developing agents described in JP-A-11-14914.
The sulfonamide phenol type color developing agents described in JP-A-6-, etc. can also be preferably used.

In the present invention, the color developing solution containing the color developing agent can be used in any pH range, but from the viewpoint of rapid processing, use at pH 9.5 to 13.0 is preferable,
The pH is more preferably in the range of 9.8 to 12.0.

The temperature of the processing solution for color development is preferably 35 to 70 ° C. The higher the temperature is, the shorter the treatment time is, which is preferable, but it is preferable that the treatment liquid is not so high in view of the stability of the treatment liquid, and the treatment at 37 to 60 ° C is preferable. The color development time is conventionally about 45 seconds, but
In the present invention, it is preferably within 35 seconds, more preferably within 25 seconds.

To the color developing solution, a known developer component compound can be added in addition to the color developing agent. Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative,
A chelating agent or the like is used.

The photographic material of the present invention is subjected to bleaching treatment and fixing treatment after color development. As the bleaching agent, an iron complex salt of polycarboxylic acid is usually preferably used. Among them, a particularly preferable compound is the bleaching agent described in JP-A-5-281684.

The bleaching agent is preferably 0.
05 g to 50 g is used, and more preferably 0.1 g to
This is an embodiment used in the range of 20 g. The temperature of the bleaching solution or the bleach-fixing solution is 2 from the viewpoint of bleaching time and bleaching fog.
The temperature is preferably 0 to 50 ° C, more preferably 25 to 45 ° C. The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less, and the pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 6 or less. .0 to 8.5. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing bath during the processing of the silver halide color photographic light-sensitive material and can be clearly distinguished from the so-called replenisher pH.

In addition to the above, halides such as ammonium bromide, potassium bromide and sodium bromide, various fluorescent whitening agents, defoaming agents, surfactants and the like should be added to the bleaching solution or bleach-fixing solution. You can also

The preferable replenishing amount of the bleaching solution or the bleach-fixing solution is 50 per 1 m ^{2 of the} silver halide color photographic light-sensitive material.
0 ml or less, more preferably 40 ml to 350
ml.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, it is possible to blow air or oxygen in the processing bath and the storage tank of the processing replenishing solution, if desired. An oxidizing agent such as hydrogen peroxide, bromate, or persulfate may be added as appropriate.

As the fixing agent used in the fixing solution or the bleach-fixing solution, thiocyanates and thiosulfates are preferably used.

The fixing solution or the bleach-fixing solution may contain, in addition to these fixing agents, a pH buffering agent composed of various salts, either alone or in combination of two or more. Further, it is desirable to add an appropriate amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride or ammonium bromide. Further, compounds known to be added to ordinary fixing solutions or bleach-fixing solutions such as alkylamines and polyethylene oxides can be added as appropriate.

In the present invention, silver may be recovered from the bleach-fixing solution by a known method. The processing time with the bleaching solution and the fixing solution is arbitrary, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, and particularly preferably 20 seconds to 1 minute and 20 seconds. is there. The processing time with the bleach-fixing solution is preferably 4 minutes or less, more preferably 10 seconds to 2 minutes and 20 seconds.

In carrying out the present invention, it is preferable that the ratio of ammonium ions to all cations in the bleaching solution or the bleach-fixing solution is 50 mol% or less, more preferably 30 mol% or less, and further preferably. It is 10 mol% or less.

From the viewpoint of improving the processing speed, it is preferable to apply forced liquid agitation to the bleaching solution and the bleach-fixing solution. The forced liquid stirring referred to here means to stir by adding stirring means. As forcible stirring means, there are JP-A 64-222259 and JP-A 1-206343.
The means described in No. 10 can be preferably used.

The crossover time from the color developing tank to the bleaching tank or the bleach-fixing tank is preferably 10 seconds or less, more preferably 7 seconds or less, which is advantageous in reducing bleaching fog. The bleaching solution and the bleach-fixing solution preferably contain substantially no acetic acid.

After bleach-fixing or fixing treatment, washing treatment is usually carried out. Further, as a substitute for the washing treatment, a stabilizing treatment may be performed.

As a developing processing apparatus used for developing the photosensitive material of the present invention, even if it is a roller transport type in which the photosensitive material is sandwiched between rollers arranged in a processing tank and conveyed, the photosensitive material is fixed to a belt. Alternatively, an endless belt method may be used, in which the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is transferred, and a spray method in which the processing solution is sprayed. Alternatively, a web method by contact with a carrier impregnated with a treatment liquid, a method by a viscous treatment liquid, or the like can be used.

In the case of processing a large amount of a light-sensitive material, it is usual to carry out a running processing by using an automatic developing machine. In this case, the smaller the replenishing amount of the replenisher is, the more preferable the processing form is from the viewpoint of environmental suitability. As a replenishment method, a treatment agent is added in the form of tablets.
The method described in No. 935 is most preferable.

The color image forming method of the present invention can be preferably applied to a heat developing system. In the present invention, heat development means exposing the exposed light-sensitive material to 50 ° C to 250 ° C.
C., preferably 60.degree. C. to 150.degree. C., to indicate a method of developing by heating. The heat treatment is carried out, for example, in JP-A-6
A method of heating and conveying while sandwiching a photosensitive material between a heat drum and a drum belt as described in JP-A-3-71850, or setting the photosensitive material between a heater and a support and simultaneously applying pressure. For example, a so-called direct heating method in which heating is performed, a method of passing a light-sensitive material between far-infrared heaters described in JP-A-4-240642, or heating by irradiation with microwaves, so-called indirect A heating method, or a method combining a direct heating method and an indirect heating method can be used.

In the heat development, for example, JP-A-63-
No. 108337 etc., a single photosensitive material is used for exposure and heat development to obtain a final image.
Formed or released by so-called one-sheet method, heat-development using a light-sensitive material and a dye image-receiving material as described in Example 1 of JP-A-6-95321 and Example 1 of JP-A-7-225461. The final image is obtained by diffusively transferring the image dye from the light-sensitive material to the dye image-receiving material,
Any of the so-called two-sheet method can be used.
In addition, a method in which a photosensitive layer and a dye image-receiving layer are laminated on one support, the image dye formed or released by heat development is diffuse-transferred from the photosensitive layer to the dye image-receiving layer, and then the photosensitive layer is peeled and removed. Can also be preferably used.

In the heat development, for example, Japanese Patent Application Laid-Open No. 2-1
As described in Example 1 of 20739, a method of developing only by heating without supplying a reaction auxiliary agent from the outside, and Example 1 of JP-A-9-5968 are described. As described above, any method may be used in which a small amount of a reaction aid (for example, water) is supplied to the photosensitive material at the time of heat development, and then heat development is performed. If no reaction aid is supplied from the outside, it is solid at room temperature,
An embodiment in which a so-called thermal solvent which is liquefied at the thermal development temperature is contained in the photosensitive material in advance is preferable. Examples of the thermal solvent include, for example, JP-A-1-227150, page 4, upper left column,
Page 9, upper right column, paragraph No. 4-289856, [001
5] to the same [0018] column and the like can be preferably used.

In the heat development, it is preferable to use a base generator from the viewpoint of improving the silver developing speed and the diffusion speed of the image dye.
9-157637, page 3, lower right to pages 6, 59-180.
537, a method using a compound capable of generating a base by thermal decomposition as described in, for example, page 4, upper left to page 7, lower left column, JP-A-8-87097, and European Patent Publication 21.
No. 0,660, U.S. Pat. No. 4,740,445, etc., a basic metal compound sparingly soluble in water in the presence of a small amount of water and a metal constituting the basic metal compound. It is possible to use a method in which a base is generated by a combination of compounds capable of a complex formation reaction using ions and water as a medium.

In the heat development, from the viewpoint of accelerating the silver development and the like, a mode in which an organic silver salt is contained in the light-sensitive material as necessary is also useful. Examples of the organic silver salt include silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring described in JP-A-49-52626, JP-A-53-362224 and the like. 52-137321
Nos. 58-118638 and the like, silver salts of compounds having an imino group, and silver salts of acetylene compounds described in JP-A-61-249044 and the like can be preferably used.

In the heat development, it is preferable to use a dye mordant in combination from the viewpoint of reducing image bleeding and fading when the final image is stored. As the dye mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used, and for example, the compounds described in paragraph Nos. [0057] to [0060] of JP-A-9-5968 are preferably used. You can

When the light-sensitive material of the present invention is used for heat development, a compound (dye-donating substance) which forms or releases an image dye is, for example, JP-A-61-61157.
No. 61-61158, No. 62-44738, No. 62-129850, No. 62-129851, No. 6
2-169158, couplers for forming diffusible dyes described in JP-A-3-73949 and the like, JP-A-6-63
Leuco dyes described in 1-88254 and the like, azo dyes described in U.S. Pat. No. 4,235,957, and the like, or JP-A-59-60434 and 59-65839.
Nos. 59-71046, 59-87450, 59-165055 and the like, JP-A-59-
55430, 59-165054 and 59-15.
No. 4445, No. 59-116655, No. 59-124.
No. 327, No. 59-152440, No. 64-1354.
No. 6, JP-A-6-51474 and the like can be preferably used, for example, compounds capable of forming an image dye in reverse correspondence to silver development.

In addition, for example, Japanese Patent Laid-Open No. 2-293753.
No. 2-308162, etc., and a photosensitive material using a microcapsule containing the above-mentioned dye-donor substance, and a polymerization reaction is carried out in an imagewise or reverse imagewise manner by heat development. Cure the microcapsules,
A heat development method in which an image is formed by changing the diffusion speed of the image dye or the physical strength of the binder can also be used.

The light-sensitive material of the present invention may also have a mode in which a developing agent or its precursor is incorporated. The developing agent contained in the light-sensitive material is required to be stable during storage of the light-sensitive material and not to unnecessarily reduce the silver salt. As a developing agent satisfying such requirements, a paraphenylenediamine-based developing agent described in JP-A-62-288835 and JP-A-9-15 can be used.
No. 806, etc., sulfonamide phenol-based main drug,
JP-A-5-241282, JP-A-8-234388, JP-A-8-286340, JP-A-9-152700, and JP-A-9-1.
52701, 9-152702, 9-1527.
No. 03, No. 9-152704 and the like, hydrazine-based main agents, JP-A Nos. 7-202002 and 8-234390.
The hydrazone-based main drugs described in the publications and the like can be mentioned.

When the light-sensitive material of the present invention contains a developing agent, development by an activator treatment can be preferably used in addition to the above-mentioned heat development treatment. Activator processing refers to a processing method in which development processing is carried out with a processing solution (activator solution) that does not contain a color developing agent, and compounds necessary for color development are incorporated in advance in the light-sensitive material. The activator solution in this case is characterized in that it does not contain the color developing agent contained in the usual color developing solution components, and may contain other components such as alkali and auxiliary developing agents. Regarding the activator treatment, European Patent Nos. 545,491A1 and 565,565 are given.
It is illustrated in publicly known documents such as 165A1.

[0107]

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

Example 1 << Preparation of silver halide emulsion >> [Preparation of blue-sensitive silver halide emulsion] 2 kept at 40 ° C.
% (A1 solution) and (B1 solution) described below were simultaneously added to 1 liter of a 1% aqueous gelatin solution over 30 minutes while controlling pAg to 7.3 and pH to 3.0. Then, the following (C1
Solution) and (D1 solution), pAg is 8.0 and pH is 5.5.
The temperature was controlled at 150 ° C, and the simultaneous addition was performed over 150 minutes. Furthermore, the following (E1 solution) and (F1 solution) had pAg of 8.0 and pH.
Was controlled at 5.5 and simultaneously added over 30 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using a sulfuric acid or sodium hydroxide aqueous solution.

(Solution A1) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B1) Silver nitrate 10 g Water was added to 200 ml (Solution C1) Sodium chloride 71.9 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag potassium bromide 0.7 g Water added 420 ml (D1 liquid) Silver nitrate 210 g Water added 420 ml (E1 liquid) Sodium chloride 30.8 g Potassium bromide 0.3 g Water added 180 ml (F1 solution) Silver nitrate 90 g Water added 180 ml After the addition of each of the above solutions was completed, a 5% aqueous solution of Demol N manufactured by Kao Atlas and magnesium sulfate 20 % Desalination, then mixed with gelatin aqueous solution,
Average particle size 0.64 μm, variation coefficient of particle size distribution 0.07,
EMP-1A which is a monodisperse cubic emulsion having a silver chloride content of 99.5 mol% was prepared.

Next, in the preparation of the above EMP-1A,
(A1 solution) and (B1 solution) addition time, (C1 solution) and (D
(1 solution) and (E1 solution) and (F1 solution) addition time were changed in the same manner, but the average particle size was 0.50 μm, the variation coefficient of the particle size distribution was 0.07, and silver chloride was added. EMP- which is a monodisperse cubic emulsion having a content of 99.5 mol%.
1B was prepared.

Next, the above-prepared EMP-1A was chemically sensitized at 60 ° C. using the following compounds.
After chemically sensitizing EMP-1B in the same manner, the sensitized EMP-1A and EMP-1B were mixed in a silver ratio of 1: 1 to prepare a blue-sensitive silver halide emulsion ( Em
-B1) was prepared.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye: BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB- 1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole (green sensitive silver halide Preparation of Emulsion) In the preparation of EMP-1A, the addition time of (A1 solution) and (B1 solution), (C1 solution) and (D1 solution) and (E1 solution) and (F1 solution) was changed. Except that the change in the same manner, the average particle diameter of 0.50μ
m, coefficient of variation 0.08, EMP-2A which is a monodisperse cubic emulsion having a silver chloride content of 99.5%, and an average grain size of 0.4.
EMP-2B, which is a monodisperse cubic emulsion having a silver chloride content of 5 μm and a silver chloride content of 99.5 mol%, was prepared.

The above EMP-2A was chemically sensitized at 60 ° C. using the following compounds. Also, the above EMP-2B
Similarly, after chemically sensitizing, the sensitized EMP-
2A and EMP-2B were mixed in a silver amount of 1: 1 to prepare a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye: GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) In the preparation of EMP-1A, The average particle size was 0.40 μm in the same manner except that the addition times of (A1 solution) and (B1 solution), (C1 solution) and (D1 solution), and (E1 solution) and (F1 solution) were changed.
m, variation coefficient 0.08, EMP-3A which is a monodisperse cubic emulsion having a silver chloride content of 99.5%, and an average grain size of 0.4.
EMP-3B, which is a monodisperse cubic emulsion having a silver chloride content of 2 μm and a silver chloride content of 99.5 mol%, was prepared.

The above-mentioned EMP-3A was chemically sensitized at 60 ° C. using the following compounds. Also, the above EMP-3
Similarly, B was chemically sensitized and then EMP sensitized
-3A and EMP-3B were mixed in a silver amount of 1: 1 and
A red-sensitive silver halide emulsion (Em-R1) was prepared.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer: STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye: RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye: RS-2 1 × 10 ^-4 mol / mol AgX stabilizer : SS-1 2.0 × 10 ^-3 mol / mol AgX

[0117]

[Chemical 3]

<< Preparation of silver halide color photographic light-sensitive material >> [Preparation of Sample 101] The surface-treated anatase type titanium oxide of 15 mass% was applied to the emulsion layer coated surface of a paper pulp having a basis weight of 180 g / m ² . The high-density molten polyethylene dispersed in the content is laminated, and the back side of the high-density polyethylene-laminated reflective support is subjected to corona discharge treatment to form a gelatin undercoat layer. Each photographic constituent layer was coated to prepare Sample 101 which is a silver halide color photographic light-sensitive material.

Incidentally, (H-1) and (H-2) were added as hardeners to the second, fourth and seventh layers. In addition, SU is used as a surfactant for dispersing the coupler in each layer.
-1 was added as a coating aid for adjusting the surface tension, and surfactants (SU-2) and (SU-3) were added. In addition, a fungicide (F-1) was added to each layer so that the total amount was 0.04 g / m ² . The silver halide emulsions shown in the table are shown in terms of silver.

[0120]

[Table 1]

[0121]

[Table 2]

Details of each additive used for the preparation of Sample 101 are as follows. SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sulfosuccinate / sodium SU-3: di (2,3,3,4,4,4) sulfosuccinate
5,5, -octafluoropentyl) -sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4 -Dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di- sec-Tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone Image stabilization Agent A: Pt-octylphenol image stabilizer B: Poly (t-butyl) Acrylamide)

[0123]

[Chemical 4]

[0124]

[Chemical 5]

[0125]

[Chemical 6]

[0126]

[Chemical 7]

[0127]

[Chemical 8]

[Production of Samples 102 to 111] Next, in the production of Sample 101, the silver halide emulsion (Em-B1) used in the first layer and the silver halide emulsion (Em-G1) used in the third layer were prepared. ) And the chemical sensitization conditions of the silver halide emulsion (Em-R1) used in the fifth layer (chemical sensitization temperature, time,
Samples 102 to 111 were prepared in the same manner, except that the additive addition timing) and the mixing ratio of the silver halide emulsion were appropriately controlled so that the effective gradation region (VE) as shown in Table 3 was obtained. It was made.

<< Evaluation of silver halide color photographic light-sensitive material >> The samples 101 to 111 thus prepared were evaluated A and B according to the following methods.

(Evaluation A) Each of the above-prepared samples was processed with 540
Wedge exposure was performed for 0.5 seconds using a 0 ° K light source, and development processing was performed according to the following development processing step 1. Each reflection density of each step of the gray step image thus obtained was measured using a densitometer PDA-65 (manufactured by Konica), and the horizontal axis-exposure amount (LogE), the vertical axis-reflection density ( A characteristic curve consisting of D) was created. Next, for each color image, the differential value of the density with respect to the exposure amount was calculated for each step to obtain the maximum point gamma.

(Evaluation B) The exposure apparatus was a sensitometer for high-intensity xenon flash exposure (SX-20 manufactured by Yamashita Denso Co., Ltd.).
Type), and combined with a Ratten filter, the exposure amount was adjusted appropriately so that a gray step image was obtained, and the exposure time was set to 10 seconds through the optical wedge for sensitometry.
^-After exposure for ⁶ seconds, the same development processing and reflection density measurement as in Evaluation A above are performed, and for each color image, the differential value of the density with respect to the exposure amount is calculated for each step to obtain the maximum point gamma, and An exposure amount area (effective gradation area) where the point gamma is 1.0 or more was obtained.

(Calculation of ΔLogE) Evaluations A and B above
In each of the characteristic curves obtained in, the difference in the position of the exposure amount (LogEd, LogEa) showing the maximum point gamma,
That is, in the characteristic curve, when one characteristic curve is slid so that the points of D = 0.8 overlap and the two characteristic curves are superposed, the exposure amount that gives the maximum point γ on the characteristic curve in the evaluation A. Point (LogEa) and evaluation B
The difference ΔLogE value from the exposure dose point (LogEd) that gives the maximum point γ on the characteristic curve was calculated.

(Development Treatment) <Development Treatment Step 1> Treatment Step Temperature Time Color development (CDC-1) 37.0 ± 0.5 ° C. 45 seconds Bleach-fixing (BF-1) 35.0 ± 2.5 ° C. 45 Second Stabilization 35 to 39 ° C. 45 seconds Drying 60 to 80 ° C. 30 seconds (Development processing solution composition) <Color developing solution (CDC-1)> Pure water 800 ml Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.02 g Potassium chloride 4. 5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.0 g N, N-diethylhydroxylamine 5.6 g triethanolamine 10.0 g diethylenetriamine Sodium pentaacetate 2.0 g Potassium carbonate 30 g Water was added to bring the total volume to 1 liter. Was adjusted to pH 10.1 with potassium hydroxide.

<Bleach-fixing solution (BF-1)> Pure water 700 ml Diethylenetriamine pentaacetate ammonium dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3 , 4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make the total amount 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing liquid> Pure water 800 ml o-Phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Magnesium sulfate heptahydrate 0.2 g Polyvinylpyrrolidone 1.0 g Nitrilotriacetic acid trisodium salt 1.5 g of water was added to bring the total amount to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or potassium hydroxide.

(Evaluation of Digitally Exposed Image) In the exposure apparatus used in the above evaluation B, a calibration operation was performed so that an image could be output for each sample, and the LUT
After creating a character image and live-action scene (landscape, person)
Output an image containing.

<Evaluation of Output Image> The print image created as described above was visually observed by 20 test subjects, and the reproducibility of the characters (black tightness, edge cut, color shift of character outline and white spots) was observed. The presence or absence of crushed parts) and the natural finish of the scene image were evaluated. The evaluation is
The higher the image quality was, the higher the score (100 points at maximum) was scored, and the average value of the evaluations of 20 people was calculated. It is shown that the higher the average point is, the more excellent the image reproducibility is, the less the scanning unevenness is, and the more beautiful the print can be obtained regardless of the change of the exposure resolution (the change of the exposure device).

(Evaluation of analog exposure image) A color negative film (manufactured by Konica) in which an image including the above-mentioned character image and a live-action scene (landscape, person) was photographed using an NPS858 type machine which is a minilab manufactured by Konica. An exposure process was performed using Centuria 100), and the same evaluation as in the digital exposure was performed.

Table 3 shows the results obtained as described above.

[0140]

[Table 3]

As is clear from Table 3, ΔLo of the present invention
It can be seen that the sample having a gE of 0.1 or less produces a preferable image in both digital exposure and analog exposure, as compared with the comparative product. Further, in the sample satisfying the requirement of the present invention that the effective gradation region of each color image is 0.84 or less, a particularly preferable image is obtained at the time of digital exposure from the viewpoint that the character outline is reproduced sharply. However, it was found that when ΔLogE is 0.1 or less, a preferable image can be obtained particularly in both digital exposure and analog exposure.

Example 2 << Preparation of Samples 201 to 211 >> In preparation of Sample 101 of Example 1, the high boiling point solvents of the first layer, the third layer and the fifth layer were changed as shown in Table 4. Of the silver halide emulsion (Em-B1) used in the first layer, the silver halide emulsion (Em-G1) used in the third layer, and the silver halide emulsion (Em-R1) used in the fifth layer. Chemical sensitization conditions (chemical sensitization temperature, time, addition timing of additives) and the mixing ratio of silver halide emulsion were appropriately controlled, and changed to obtain a ΔLogE value as shown in Table 4 in the same manner. Samples 201 to 211 were produced. The high boiling point solvent was added in an amount equivalent to the mass.

<< Characteristic Evaluation of Each Sample >> With respect to Samples 201 to 211 produced as described above, exposure and development were performed in the same manner except that the temperature and relative humidity at the time of exposure were changed as shown in Table 4. After the treatment, the digitally exposed image and the analogly exposed image were evaluated, and the specific maximum density (Dmaxd) exposed at the maximum energy of 10 ⁻⁶ seconds was measured.

Table 4 shows the results obtained as described above.

[0145]

[Table 4]

As can be seen from Table 4, the samples of the present invention having ΔLogE of 0.1 or less gave favorable images over both the digital exposure and the analog exposure as compared with the comparative product. . In addition, the sample using the high boiling point solvent represented by the general formula (1) according to the present invention is surprisingly improved in color development in short-time exposure, increased in maximum density, and more tight. It turns out that an image is obtained. Further, it was confirmed that the sample of the present invention can obtain a high image even under severe conditions in which it is difficult to obtain a good image because the temperature and humidity during exposure largely fluctuate.

Example 3 Samples 101, 102, 105 and 10 prepared in Example 1
6 was used, except that the color development processing conditions were changed to pH 10.50, temperature 39.0 ± 0.5 ° C., and processing time from 45 seconds to 15 seconds. 1
The digital exposure image and the analog exposure image were evaluated in the same manner as in the method described in 1., and the obtained results are shown in Table 5.

[0148]

[Table 5]

As is clear from Table 5, in Comparative Examples, when the color development time was shortened, the image quality of the digitally exposed image in which the exposure time was shortened remarkably deteriorated.
Samples 105 and 106 having LogE of 0.1 or less show almost no image deterioration even when the color development time is shortened, and are stable in a wide exposure time range from an extremely short exposure time to a normal exposure time. I got a beautiful image.

[0150]

According to the present invention, a silver halide color photographic light-sensitive material having high image quality, which is excellent in stability against changes in exposure time, changes in temperature and humidity during exposure, shortening of processing time, and excellent in color developability, and the same. A color image forming method can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H016 AB02 AC00 BD00 BK00                 2H023 CD13

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one yellow color image forming layer, a magenta color image forming layer and a cyan color image forming layer each containing a photosensitive silver halide on a support. 10 ^-6 per pixel
After exposure with an exposure time of 2 seconds, development processing was performed, and an exposure amount (LogEd) that gives the maximum point γ (γmd) of each color image obtained, and after exposure with an exposure time of 0.5 seconds per pixel A silver halide characterized by having a difference ΔLogE (LogEd-LogEa) of 0.1 or less with respect to an exposure amount (LogEa) that gives the maximum point γ (γma) of each color image obtained by development processing. Color photographic light-sensitive material. 2. A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer each containing a photosensitive silver halide on a support, 10 per pixel
^-10 seconds or more 10 ^- was exposed in ³ seconds or less exposure time, the effective tone area of the color image obtained by developing (VE) are each 0.65 to 0.84 or less in each color image forming layer 2. The silver halide color photographic light-sensitive material according to claim 1, wherein 3. At least one of the yellow image forming layer, the magenta image forming layer, and the cyan image forming layer,
The silver halide color photographic light-sensitive material according to claim 1 or 2, containing a compound represented by the following general formula (1). [Chemical 1] [In the formula, R ₁ , R ₂ and R ₃ each represent a substituent and may be the same or different. ] 4. A color image forming process, wherein the silver halide color photographic light-sensitive material according to any one of claims 1 to 3 is subjected to development processing in a processing time of a color development step of 25 seconds or less. Method. 5. An image formed on the silver halide color photographic light-sensitive material according to any one of claims 1 to 3 has a scene image and a character image in the same image. Forming method.