JP2001188324A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in rapid processability and production stability and excellent in the shad depiction of the high density part of a color print obtained by scanning exposure. SOLUTION: The silver halide color photographic sensitive material contains an emulsion with silver halide grains having >=95 mol% silver chloride content in a photosensitive silver halide emulsion layer and satisfies the relations of the expressions 0.65<=D1'/D1<=0.85 and 1.1<=log(E2/E1)<=1.4 with respect to each characteristic curve obtained by exposing and color-developing the sensitive material. In the expressions, D1 is a density obtained in the case of exposure with 10 times as much light exposure as the light exposure required to obtain (the density of the unexposed part)+0.02 on a characteristic curve obtained by exposure for 10-1 sec exposure time; D1' is that on a characteristic curve obtained by exposure for 10-4 sec exposure time: E1 is the light exposure required to obtain (the density of the unexposed part) +0.02 on the characteristic curve obtained by exposure for 10-4 sec exposure time; and E2 is the light exposure required, on the same characteristic curve, to obtain a density 0.92 time the maximum density on the characteristic curve obtained by exposure for 10-1 sec exposure time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material, which is excellent in rapid processing, excellent in shading of high density portions in scanning exposure, and suitable for surface exposure. The present invention relates to a silver halide color photographic material.

[0002]

2. Description of the Related Art Color photography, which has become widespread today, has become more and more quickly and easily available due to improvements in photosensitive materials themselves and advances in processing techniques.
In the field of color printing, in particular, centralized processing methods at production bases equipped with high-speed printers for mass production called color labs and large-scale processing equipment, and distributed processing using small printer processors called mini labs installed at stores Due to the development of the method, production according to various purposes is performed.

[0003] For rapid processing, see US Patent 4,840,
No. 878 discloses a technique for processing a color photographic light-sensitive material using a silver halide emulsion having a high silver chloride content with a color developing solution substantially free of sulfite ions and benzyl alcohol. Photosensitive materials using high silver chloride emulsions and their processing methods have been put into practical use,
Color prints are becoming available more quickly and easily.

In recent years, in addition to conventional printing by surface exposure, a color print is provided from image data obtained by digitizing a negative image and a positive image by a scanner. By digitizing images, corrections such as gradation correction, dodging, and lettering when creating postcards can be performed on a computer monitor without the production of squirrel film, improving the productivity and quality of color prints. Has contributed. Further, it is also possible to receive image data through the Internet to produce a color print, and it is considered that the color print will be further spread in the future. In order to obtain a color print from digital image data, a light source such as a cathode ray (CRT) or a laser is used instead of a surface exposure through a normal negative film.
Scanning exposure is performed pixel by pixel.

[0005] As described above, in the color print manufacturing method, printing by conventional surface exposure and printing by scanning exposure are performed, and color print materials dedicated to each exposure method have been put to practical use. For this reason, two types of color print materials are required in the field of color print production, but it is convenient if only one type is sufficient. Therefore, provision of color print materials suitable for both surface exposure and scanning exposure is provided. Is desired. As a photosensitive material having suitability for both surface exposure and scanning exposure, U.S. Pat. No. 5,869,228 contains an iron ion intensively in a high silver chloride emulsion grain surface region and contains an o-hydroquinone compound or a p-hydroquinone compound. A technique has been disclosed in which a photographic material having the same photographic performance as surface exposure is obtained in scanning exposure by incorporating it in a photosensitive material. The present inventor has studied a photosensitive material to which this technique is applied. As a result, in a color print obtained by scanning exposure, a problem has arisen that the shading of a high density portion becomes unnaturally large. Although the scanning exposure data is digitized, it is possible to correct only the digital data of the shaded portion, but it takes time and effort to correct the data, which is practically unacceptable in a normal color laboratory.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is suitable for surface exposure and which is excellent in rapid processing, excellent in shading of a high density portion of a color print obtained by scanning exposure. Is to provide.

[0007]

The present inventors have made intensive studies and found that the objects of the present invention can be achieved by the following means. (1) A silver halide having at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler on a support. A color photographic light-sensitive material, wherein at least one of the light-sensitive silver halide emulsion layers contains an emulsion having silver halide grains having a silver chloride content of 95 mol% or more, and the light-sensitive material is subjected to color development after exposure. A silver halide color photographic light-sensitive material, characterized by satisfying the following relations with respect to each characteristic curve obtained by the above. 0.65 ≦ D1 ′ / D1 ≦ 0.85 1.1 ≦ log (E2 / E1) ≦ 1.4 D1: In the characteristic curve obtained by exposing at an exposure time of 10 ⁻¹ sec, the density of the unexposed portion + 0 Density obtained when exposure is performed at an exposure amount that is 10 times the exposure amount required to obtain a density of 2.02. D1 ': Density of an unexposed portion in a characteristic curve obtained by exposure at an exposure time of 10 ^-4 seconds. Density obtained when exposure is performed at an exposure amount 10 times the exposure amount required to obtain a density of +0.02 E1: density of an unexposed portion in a characteristic curve obtained by exposure at an exposure time of 10 ^-4 seconds Exposure amount required to obtain a density of +0.02 E2: In the characteristic curve obtained by exposing at an exposure time of 10 ^-4 seconds, the maximum density 0 in the characteristic curve obtained by exposing at an exposure time of 10 ^-1 second Exposure amount required to obtain .92 times the density (2) The characteristic curve obtained by exposing the photosensitive material with red light and then color-developing satisfies the above relationship The silver halide color photographic light-sensitive material as described in (1) above, (3) The emulsion according to (1) or (2), wherein the emulsion contains silver halide grains having a silver chloride content of 95 mol% or more and containing at least two kinds of Group VIII metal complexes of the periodic table. The silver halide color photographic light-sensitive material described in the above.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The silver halide color photographic light-sensitive material of the present invention is defined by characteristics relating to each characteristic curve obtained as follows.
That is, the photosensitive material is subjected to sensitometric gradation exposure with blue light, green light or red light, and then subjected to color development processing, and the color density is measured. Can be obtained. The exposure time is 10 ^-1 seconds and 10 ^-4
By setting to seconds, characteristic curves corresponding to 10 ^-1 seconds and 10 ^-4 seconds, respectively, can be obtained. In the photosensitive material of the present invention,
With respect to any of the characteristic curves corresponding to the blue light, green light or red light obtained in this way, it is necessary to satisfy the following relationship, and the characteristic curve corresponding to the red light must satisfy the following relationship. More preferred.

[0009] 0.65≤D1 '/ D1≤0.85 1.1≤log (E2 / E1) ≤1.4 D1: In the characteristic curve obtained by exposing with an exposure time of 10 ^-1 second, an unexposed portion Density obtained when exposure is performed at an exposure amount 10 times the exposure amount necessary to obtain a density of +0.02 D1 ': In the characteristic curve obtained by exposing at an exposure time of 10 ^-4 seconds, unexposed Density obtained when exposure is performed at an exposure amount 10 times the exposure amount required to obtain a density of +0.02 parts, E1: unexposed in the characteristic curve obtained by exposing at an exposure time of 10 ^-4 seconds Exposure amount required to obtain a density of +0.02 in the density part E2: In the characteristic curve obtained by exposing at an exposure time of 10 ^-4 seconds, the maximum in the characteristic curve obtained by exposing at an exposure time of 10 ^-1 second Exposure required to obtain 0.92 times the density

If this log (E2 / E1) is smaller than 1.1,
The shading of the high-density portion of the image obtained by the scanning exposure becomes unnaturally strong. Further, when log (E2 / E1) is larger than 1.4, the image obtained by the scanning exposure has a weak shadow in a high-density portion, resulting in an image with no tightness. On the other hand, lo
When g (E2 / E1) is in the range of 1.1 or more and 1.4 or less specified in the present invention, the tightness of the shadow in the high density portion of the image obtained by the scanning exposure is good. More preferably log (E2 / E1)
Is not less than 1.15 and not more than 1.35. Even if log (E2 / E1) is within the range specified in the present invention, if D1 '/ D1 is larger than 0.85 or smaller than 0.65, the connection of shadows is poor and a light shade may be drawn. Can not. Therefore,
This D1 '/ D1 needs to be set within the range defined in the present invention. More preferably, D1 '/ D1 is 0.68 or more and 0.8.
2 or less.

In the present specification, unless otherwise specified, all exposures defined only by exposure seconds are surface exposures. The light source used in the present invention is not particularly limited as long as the illuminance required for each exposure can be obtained, and an ordinary halogen lamp, mercury lamp, or the like can be used. Exposure for obtaining a characteristic curve for light having a specific wavelength as defined in the present invention can be performed by extracting the specific wavelength region through a color filter by a conventional method and exposing the light source itself, It may contain light having a wavelength that is sensitive to a photosensitive layer other than the photosensitive layer that is sensitive to the specific wavelength region.

In order to obtain the characteristics of the characteristic curve defined in the present invention, it is preferable to have two or more silver halide emulsions having different photographic sensitivities in the same silver halide emulsion layer. When only one type of emulsion is contained in the silver halide emulsion layer, a color density of 60% of the maximum density is obtained in each characteristic curve obtained by color development after exposure for 10 ^-1 or 10 ^-4 seconds. And the exposure amount (E ') required to obtain a density of 10% of the maximum density.
log (1 / E) is the medium density sensitivity, and log (1 / E ') is the low density sensitivity. In this case, of the two or more kinds of emulsions contained in the same silver halide emulsion layer, the emulsion having the highest sensitivity and the emulsion having the lowest sensitivity are exposed at 10 ^-1 second exposure at any of the above low and medium densities. Also preferably has a sensitivity difference of 0.05 to 0.60, more preferably 0.10 to 0.50. Further, it is preferable that the difference in sensitivity in the medium density portion in the exposure at 10 ^-4 seconds is 0.05 or more larger than the difference in sensitivity in the middle density portion in the exposure at 10 ^-1 second.
Furthermore, the difference between the low-density area sensitivity difference in the 10 ^-4 second exposure and the low-density area sensitivity difference in the 10 ^-1 second exposure is almost the same (0.0
5 or less).

To change the photographic sensitivity of a silver halide emulsion, it is customary to change the size of the silver halide emulsion grains. Generally, the photographic sensitivity is increased by increasing the particle size, and the photographic sensitivity can be reduced by decreasing the particle size. These silver halide emulsion grains having different sizes are more preferably monodisperse grains. In order to obtain a silver halide emulsion whose photographic characteristics at each exposure time have the characteristics specified in the present invention, in addition to changing the size of silver halide emulsion grains as described above, chemical Adjustment of dosage,
Adjustment of chemical sensitization conditions (pAg, pH, temperature, time, etc.),
And / or a silver halide emulsion preferably contains a metal complex of Group VIII of the periodic law, and is used in combination with a technique such as adjusting the amount thereof. Among these methods, it is more preferable to use a method in which a silver halide emulsion contains a group VIII metal complex of the periodic law in combination. For example, in the case of a silver halide emulsion layer containing a periodic group VIII metal complex and two chemically sensitized silver halide emulsions having different grain sizes, the amount of the periodic group VIII metal complex on the smaller size side The log (E2 / E1) can be changed without changing the value of D1 ′ / D1 by changing the value of D1 ′ / D1, and by changing the amount of the periodic group VIII metal complex on the large size side,
The value of D1 '/ D1 can be changed without changing the value of g (E2 / E1) so much. That is, D1 ′ / D1 and l are obtained by separately changing the amount of the Group VIII metal complex contained in the small-size and large-size silver halide emulsions.
og (E2 / E1) can be changed almost independently.

In the silver halide color light-sensitive material of the present invention, a metal complex of Group VIII of the periodic table is preferably contained in the silver halide grains, and the metal complex is dispersed in a dispersion medium during the formation of the silver halide grains. Gelatin or polymer with protective colloid properties) solution, halide solution,
When it is present in a silver salt solution or another aqueous solution, it can be contained in silver halide grains. When a silver bromide localized phase is formed by adding silver bromide fine particles and / or silver chlorobromide fine particles, a silver bromide localized phase can be formed by using fine particles containing a metal complex in advance. Metal ions can be selectively contained therein. In the present invention, the silver halide grains in the photosensitive silver halide emulsion layer preferably contain a metal complex of Group VIII of the periodic table, and may be contained in the silver halide grains in the red photosensitive emulsion layer. More preferred. These metal complexes include, for example, complexes of iron, cobalt, nickel, ruthenium, rhodium, iridium and platinum. Preferably, a complex of iron, iridium or ruthenium is used. More preferably, the iron or ruthenium complex is contained in the surface layer of 50% or less of the volume of the silver halide grains in a concentrated manner so as to be larger than the other silver halide grains. 50% or less of the particle volume refers to a surface portion corresponding to a volume of 50% or less of the volume of one particle. This surface portion is more preferably at most 40%, more preferably at most 20%. The iridium complex is preferably used in the silver bromide rich phase, as described above, in addition to being added during grain formation and contained in the grains.

The Group VIII metal complex used in the present invention is not limited to one kind, and it is preferable to use two or more kinds. In the present invention, it is preferable to use a complex of iron and iridium or a complex of ruthenium and iridium in combination. iron,
Specific examples of compounds used when ruthenium and iridium complexes are contained in silver halide grains are shown below, but the present invention is not limited to these.

(Iron compound) Iron (II) arsenate, iron bromide (I
I), iron (II) carbonate monohydrate, iron (II) chloride, iron (II) citrate, iron (II) fluoride, iron (II) formate, iron (II) gluconate, iron (II) hydroxide ( II), iron iodide (II), iron lactate (I
I), iron (II) oxalate dihydrate, iron (II) succinate,
Iron (II) sulfate heptahydrate, iron (II) thiocyanate trihydrate, iron (II) nitrate hexahydrate, ammonium iron (II) nitrate, basic iron (III) acetate, iron albumate ( III), ammonium iron (III) acetate, iron (III) bromide, iron (III) chloride,
Iron (III) chromate, Iron (III) citrate, Iron (II) fluoride
I), iron (III) formate, glycero-iron (III) phosphate, iron (III) hydroxide, iron (III) acid phosphate, iron (III) nitrate nonahydrate, iron (III) phosphate, Iron (III) pyrophosphate, sodium iron (III) pyrophosphate, iron (III) thiocyanate, iron (III) sulfate nonahydrate, ammonium (III) sulfate, iron (III) guanidinium sulfate, iron citrate ( III) Ammonium, potassium hexacyanoferrate (II) trihydrate, potassium pentacyanoammineiron (II), sodium ethylene (III) ethylenedinitrilotetraacetate, potassium hexacyanoferrate (III).

(Ruthenium compound) ruthenium (VI) fluoride, ruthenium (IV) chloride pentahydrate, potassium hexachlororuthenate (IV), ruthenium (III) chloride,
Ruthenium (III) bromide, ruthenium (III) iodide, hexaammine ruthenium (III) bromide, chloropentaammine ruthenium (III) chloride, hexaammine ruthenium (II) chloride, potassium hexacyanoruthenate (II) Trihydrate.

(Iridium-containing substances) Potassium hexachloroiridate (IV), hexabromoiridium (IV)
Potassium citrate, ammonium hexachloroiridate (IV), iridium (III) bromide tetrahydrate, iridium (III) iodide, potassium hexachloroiridium (III) trihydrate, hexabromoiridium (III) acid Potassium, potassium tris (oxalato) iridate (III) tetrahydrate, potassium hexacyanoiridium (III), iridium (II) chloride.

Among these compounds, hexacyanoferrate (II), hexacyanoferrate (III), hexacyanoruthenium (II), hexachloroiridium (IV), and hexabromoiridium ( IV), hexachloroiridium (III) and hexabromoiridium (III) are preferably used. These VIII
The addition amount of the group metal ion varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-3 mol per mol of silver halide. More preferably, the amount is 10 ^{-8 to} 5 × 10 ^-4 mol per mol of silver halide.

In addition to the Group VIII metal complex of the periodic table, copper,
Metals such as gold, zinc, cadmium or lead may be included. These metals may be present in a layer containing a Group VIII metal, or may be contained in a layer containing no Group VIII metal, depending on the purpose. The addition amount of these metal ions varies widely depending on the purpose, but is generally preferably from 10 ^{< -9>} to 10 ^{<-2 >} mol per mol of silver halide.

The silver halide emulsion used in the present invention is:
Subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.

This silver halide emulsion is preferably subjected to gold sensitization by a conventional method. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates or gold thiosulfates can be used. The addition amount of these compounds can vary widely depending on the case, but is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻⁷ per mol of silver halide.
× 10 ^-3 mol, more preferably 1 × 10 ^-6 to 1 × 10 ^-4
Is a mole.

In the present invention, gold sensitization is carried out by other sensitization methods,
For example, it may be combined with sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

The silver halide color light-sensitive material of the present invention comprises
At least one of the light-sensitive silver halide emulsion layers contains an emulsion having silver halide grains having a silver chloride content of 95 mol% or more. Preferably, the red photosensitive emulsion layer contains an emulsion having silver halide grains having a silver chloride content of 95 mol% or more. More preferably, the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer contain an emulsion having silver halide grains having a silver chloride content of 95 mol% or more. The silver chloride content is preferably at least 96 mol%, more preferably at least 97 mol% and less than 100 mol%.

In the present invention, the silver chloride content is 95 mol%.
The above silver halide grains are preferably provided with a silver bromide-rich phase, and the silver bromide-rich phase of the silver halide grains has at least a total silver bromide content in the silver bromide-rich phase. It is preferable to form a localized phase of 10 mol% or more by epitaxial growth. The total content of silver bromide in the silver bromide rich phase is preferably at least 10 mol%, but if the silver bromide content is too high, desensitization may occur when pressure is applied to the light-sensitive material, Variations in the composition of the processing solution may impart undesired characteristics to the photographic material, such as a significant change in sensitivity and gradation. Taking these points into consideration, the silver bromide content of the silver bromide rich phase is preferably in the range of 10 to 60 mol%,
A range of 50 mol% is most preferred. The silver bromide content of the silver bromide-rich phase can be analyzed using an X-ray diffraction method (for example, described in “New Experimental Chemical Account 6, Structural Analysis”, edited by The Chemical Society of Japan). . The silver bromide rich phase is preferably composed of 0.1 to 5 mol% of silver, preferably 0.3 to 4 mol% of the total silver constituting the silver halide grains used in the present invention. More preferably, it is composed of

As is generally well known, the steps of preparing a silver halide emulsion in the present invention include a step of forming silver halide grains by a reaction between a water-soluble silver salt and a water-soluble halide, a step of desalting, and a step of chemical ripening. Consisting of The application of the silver bromide-rich phase can be carried out in any of the above steps, but is preferably carried out after the desalting step, and particularly preferably after the desalting step and before the end of chemical sensitization. Among the rich bromide rich phases, there are VIII compounds such as IrCl ₆ ^2-
It is preferable to contain a group metal complex ion. When an iridium compound is contained in the silver bromide rich phase of the silver halide emulsion grains, the rich phase is preferably deposited together with at least 50 mol% of the total iridium added during the preparation of the silver halide grains. More preferably, the rich phase is deposited with at least 80 mol% of the total iridium added, most preferably with the total iridium added. Here, to deposit the rich phase together with iridium means to supply the iridium compound simultaneously with, just before, or immediately after the supply of silver or halogen for forming the rich phase. When a silver bromide-rich phase is formed by mixing silver halide fine grains having a smaller average grain size than the silver halide host grains and having a high silver bromide content and then ripening, the silver bromide content It is preferred that the iridium salt is previously contained in the silver halide fine grains having a high content.

The silver halide grains used in the present invention are:
Even if the outer surface has a (100) plane, (11)
1) A cube having mainly (100) planes may be a plane having a plane, a plane having both planes, or a plane including higher-order planes. Or a tetradecahedron. The size of the silver halide grains used in the present invention may be within the range usually used, but the average grain size is preferably from 0.1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size variation coefficient representing the degree of monodispersion is a ratio (s / d) of the standard deviation (s) statistically to the average particle size (d).
Is preferably 0.2 or less, more preferably 0.15 or less. It is also preferable to use two or more kinds of monodisperse emulsions having different sensitivities in the same silver halide emulsion layer in order to obtain a required gradation.

The silver halide grains used in the present invention may have a regular crystal form such as an octahedron other than a cube or a tetradecahedron, or an irregular shape such as a sphere or a plate. Those having an irregular crystal form or those having a complex form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the regular crystal form are contained in an amount of 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. Further, besides grains having a regular crystal form, tabular grains having an average aspect ratio (diameter / circle equivalent in circle / thickness) of 5 or more, preferably 8 or more have a projected area of 50% by mass or more of all grains. Emulsions can also be preferably used. The silver halide emulsion used in the present invention is a P.I. Chi by Glafkids
miet Physique Photogfaph
iq (published by Paul Montel, 1967)
Year), G. F. Photographi by Duffin
cEmulsion Chemistry (Focal
Press, 1966); L. Zelik
Making and Coat by man et a1
ing Photographic Emulsion
(Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Various silver halide emulsions for use in the present invention may be used for the purpose of preventing fog of the emulsion or the light-sensitive material during the production process, storage or photographic processing, or stabilizing photographic performance. Compounds can be included. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
Mercaptothiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-
5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines and the like; thioketo compounds such as oxazolinethione; azaindenes;
For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene) pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like. Many compounds known as antifoggants or stabilizers can be added. Particularly preferred are mercaptotetrazoles. This is preferable because it has a function of further increasing the high illuminance sensitivity in addition to preventing fog and stabilizing.

In the silver halide color photographic light-sensitive material according to the present invention, gelatin is used as a hydrophilic binder.
If necessary, other gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, and hydrophilic colloids such as synthetic hydrophilic polymer substances such as mono- or copolymers may also be used. It can be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be any of lime-processed gelatin and acid-processed gelatin, and gelatin produced from any of bovine bone, cowhide, pork skin and the like. However, lime-processed gelatin obtained from cow bone and pig skin is preferred.

In the present invention, in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer up to the hydrophilic colloid layer farthest from the support on the side where the silver halide emulsion layer is coated from the support. Is preferably 8.0 g / g from the viewpoint of rapid processing.
m ² or less, most preferably 7.0 g / m ² or less;
0 g / m ² or more. When the amount of the hydrophilic binder is small, it is particularly effective for speeding up the color development and washing steps.

In the present invention, the silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler containing layer contains silver halide tabular grains, And at least one of the magenta coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer, which is more distant from the support. Further, from the viewpoint of accelerating color development, desilvering, and reducing residual color by a sensitizing dye, the silver halide emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers. Preferably, it is provided. Further, from the viewpoint of reducing Blix discoloration, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of the other silver halide emulsion layers.
From the viewpoint of reducing photobleaching, the cyan coupler-containing silver halide emulsion layer is preferably the lowermost layer. Each of the color forming layers for yellow, magenta and cyan has two layers or three layers.
It may consist of layers. For example, JP-A-4-75055
No., 9-114035, 10-246940,
As described in U.S. Pat. No. 5,576,159, it is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

In the silver halide emulsion layer containing the yellow coupler, the amount of the hydrophilic binder is preferably 1.55 g.
/ M ² or less, more preferably 1.45 g / m ² or less, most preferably 1.35 g / m ² or less 0.60 g / m ² or more. The silver halide emulsion preferably has a side length of 0.80 μm or less, more preferably 0.75 μm or less, and most preferably 0.70 μm or less when cubic grains are used.
0.30 μm or less, and the side length when tabular grains are used is preferably 0.40 μm or less, preferably 0.02 μm or less, more preferably 0.30 μm or less, still more preferably 0.20 μm or less, and most preferably. Is 0.15
μm or less and 0.05 μm or more. The aspect ratio of the tabular grains is preferably from 2 to 10, more preferably from 3 to 8. Further, in order to control sensitivity, gradation and other photographic performance, it is preferable to use a mixture of silver halide emulsions having different sizes and shapes.

In the present invention, the coating amount of the silver halide emulsion is preferably from 0.70 g / m ^{2 to} 0.10 g / m ^2, more preferably from 0.65 g / m ^{2 to} 0.20 g / m ^2.
m ² or more, most preferably 0.55 g / m ² 0.25
g / m ² or more.

When cubic silver halide emulsion grains are used for the cyan coloring layer and the magenta coloring layer, the side length is preferably 0.70 μm or less, more preferably 0.50 μm or less and 0.10 μm or more. .

In the present invention, the film thickness of the photographic layer structure means
It represents the thickness before processing of the photographic layer configuration above the support.
Specifically, it can be determined by any of the following methods. First, it can be determined by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with a microscope. The second method is to calculate the film thickness from the coating amount (g / m ² ) and specific gravity of each component in the photographic layer constitution. For example, the specific gravity of typical gelatin used for photography is 1.34 g / ml, the specific gravity of silver chloride is 5.59 g / ml, and other lipophilic additives are measured before coating. Thus, the film thickness can be calculated by the second method.

In the present invention, the thickness of the photographic layer is preferably 10.0 μm or less, more preferably 9.5.
μm or less, most preferably 9.0 μm or less and 3.5 μm or more.

Examples of the hydrophobic photographic material used in the present invention include oil-soluble components excluding dye-forming couplers. The oil-soluble components are lipophilic components remaining in the light-sensitive material after processing. Specific examples include a dye-forming coupler, a high-boiling organic solvent, a color-mixing inhibitor, an ultraviolet absorber, a lipophilic additive, a lipophilic polymer or polymer latex, a matting agent, and a slipping agent. It is added to the layer. Therefore, water-soluble dyes, hardeners, water-soluble additives, silver halide emulsions and the like do not fall under oil-soluble components. Usually, a surfactant is used when preparing the lipophilic fine particles, but the surfactant is not treated as an oil-soluble component in the present invention.

In the present invention, the total amount of the oil-soluble component is preferably 5.5 g / m ² or less, more preferably 5.0 g / m ^2.
m ² or less, most preferably 4.5 g / m ² or less 3.0 g /
m ² or more. In the present invention, the value obtained by dividing the mass (g / m ² ) of the hydrophobic photographic material contained in the layer containing the dye-forming coupler by the mass (g / m ² ) of the dye-forming coupler is 4.5 or less. And more preferably 3.
5 or less, and most preferably 3.0 or less.

In the present invention, the ratio of the oil-soluble component to the hydrophilic binder in the photographic layer can be set arbitrarily. The preferred ratio in the photographic layer constitution other than the protective layer is 0.05 to 1.50 by mass, more preferably 0.10 to 1.4.
0. By optimizing the ratio of each layer, the film strength, scratch resistance, and curl characteristics can be adjusted.

In the photographic material according to the present invention, a dye capable of being decolorized by a treatment described in EP-A-337,490 A2, pp. 27-76, is applied to a hydrophilic colloid layer for the purpose of improving sharpness and the like in an image. (An oxonol-based dye) so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.50 or more, or a divalent or tetravalent alcohol (for example, trimethylolethane) is added to the water-resistant resin layer of the support. ) Or the like is preferably contained in an amount of 12% by mass or more (more preferably 14% by mass or more).

The silver halide photographic light-sensitive material of the present invention includes:
In addition, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmission type support include transmission films such as cellulose nitrate film and polyethylene terephthalate, as well as 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG).
And a polyester of NDCA, terephthalic acid and EG, etc., provided with an information recording layer such as a magnetic layer is preferably used. The reflective support is particularly laminated with a plurality of polyethylene layers and polyester layers,
A reflective support containing a white pigment such as titanium oxide in at least one such water-resistant resin layer (laminate layer) is preferred.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. Further, the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent whitening agent, preferably, benzoxazole-based, coumarin-based, pyrazoline-based can be used, more preferably,
Benzoxazolyl naphthalene and benzoxazolyl stilbene fluorescent brighteners. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The above-mentioned reflection type support, silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, and yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0046]

[Table 1]

[0047]

[Table 2]

The cyan, magenta and yellow couplers used in combination in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Column 6th line to page 35, lower right column, line 11 or EP 355,660A
No. 2, page 4, lines 15-27, page 5, lines 30-28
Couplers described in the last line of the page, the 29th to 31st lines of the 45th page, the 23rd line of the 47th page to the 50th line of the 63rd page, JP-A-8-122984 and JP-A-9-222704 are also useful.
As the cyan coupler, a pyrrolotriazole coupler is preferably used.
Particularly preferred are couplers represented by the general formula (I) or (II) of the above-mentioned No. 3, couplers represented by the general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, a high-molecular redox compound described in JP-A-5-333501, Japanese Patent Application No. 9-140.
No. 719, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 37, No. 10-282615, German Patent No. 1962
White couplers described in 9142A1 and the like can be used. In particular, when increasing the pH of the developing solution to speed up the development, German Patent No. 191818686A
No. 1,980,846A1, European Patent No. 83
It is also preferable to use the redox compounds described in 9,623A1, 842,975A1, French Patent No. 2,760,460A1, and the like.

In the present invention, as an ultraviolet absorber,
It is preferable to use an ultraviolet absorber having a high molar extinction coefficient. Examples of such a compound include compounds having a triazine skeleton.
No. 55-152776, JP-A-5-1970074
Nos. 5-232630, 5-307232, 6-211813, 8-53427, and 8-23
No. 4364, No. 8-239368, No. 9-31067
No., No. 10-115598, No. 10-147577
No. 10-182621, Tokuyohei 8-501291
No. 711,804A and German Patent No. 19
Preferred are those described in U.S. Pat.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the photosensitive material, and particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .
The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the cathode ray tube has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time,
That is, a plurality of color image signals may be input to the cathode ray tube to emit light from the tube surface. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

The photosensitive material of the present invention is a second harmonic generation light source (SHG) obtained by combining a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high-density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) in which a semiconductor laser or a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

A solid-state laser using a semiconductor laser as an excitation light source
Laser or non-linear optical crystal with laser diode
In the SHG light source that is obtained by
Since it can be halved, blue light and green light can be obtained. Follow
And the spectral sensitivity maxima in the normal three wavelength regions of blue, green and red
It is possible to obtain an image using a photosensitive material having
The exposure time in such scanning exposure is such that the pixel density is 4
The pixel size when 00 dpi is set as the exposure time
Defined as the preferred exposure time is 10 ^-FourSeconds
Below, more preferably 10^-6Seconds or less.

Preferred scanning exposure systems applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5 upper left column The processing materials and processing methods described in the 17th line to the 20th line on the lower right column on page 18 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

As the method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkali agent and a developing agent, and an alkali solution containing a developing agent in the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-2343.
No. 88, No. 9-152686, No. 9-152693
JP-A-9-218814, JP-A-9-16019
The hydrazine-type compound described in No. 3 is preferred.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator liquid containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the processing of the light-sensitive material of the present invention, known materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541, and JP-A-8-234388 can be used.

In the processing of the light-sensitive material of the present invention, the color development time refers to the time from when the light-sensitive material enters the color developing solution to when it enters the bleach-fixing solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called submerged time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath.
The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called submerged time). The light-sensitive material of the present invention is preferably subjected to rapid processing, and the color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less and 6 seconds or more.

The method of drying the light-sensitive material of the present invention may be any method known in the art for rapid drying of a color light-sensitive material. For the purpose of the present invention, the color light-sensitive material is dried for 20 seconds. It is preferable that drying can be performed within 15 seconds, preferably within 15 seconds, and most preferably within 5 seconds to 10 seconds. As a drying method, either a contact heating method or a hot air blowing method may be used, but the combination of the contact heating method and the hot air blowing method enables quick drying compared to the case of using either method Is preferable. A further preferred embodiment of such a drying method is a method in which the photosensitive material is contact heated by a heat roller and then blown dry by warm air blown from the perforated plate or the nozzle group toward the photosensitive material.
In the blast drying section, the mass velocity of the hot air blown per unit area of the heat receiving area of the photosensitive material is 1000 kg / m ^2.
hr or more is preferable. Further, it is preferable that the shape of the blowing outlet is a shape having a small pressure loss, and for example, the seventh to seventh embodiments described in JP-A-9-33998 are preferable.
FIG. 15 is cited.

[0062]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Preparation of emulsion

Solution I Water 1000 ml Lime treated gelatin 58 g NaCl 63 mmol pH (with sulfuric acid added) 2.9

Liquid II 1.70 mol of silver nitrate 617 ml with water added Liquid 617 ml of III liquid NaCl 617 ml with water added 617 ml Liquid IV nitrate 0.42 mol with added water 200 ml V liquid NaCl 0.42 mol KBr 4.2 mmol hexacyanoiron (II) ) Potassium trihydrate 0.06mmol Add water and 200ml

The solution II and the solution III were simultaneously added to the solution I kept at 50 ° C. with vigorous stirring (solution addition rate of solution 6.
2 ml / min, solution III addition rate 6.9 ml / min). 22 minutes and 30 seconds after the start of the addition, the addition speed of the solution II and the solution III was accelerated.
All liquids were added. Further, the liquids IV and V were all added over 12 minutes with vigorous stirring. After keeping at 50 ° C. for 10 minutes, the temperature was lowered, and desalting, sedimentation and washing with water were performed. Furthermore, 5
The temperature was raised to 0 ° C and 170 g of lime-processed gelatin was added.
Was adjusted to 5.3 and the pAg to 7.5. To this emulsion, 0.04 mmol of sodium benzenethiosulfonate per 1 mol of silver, 0.03 m
mol, 0.015 mmol of chloroauric acid, 0.2 mmol of potassium thiocyanate and 0.00 of triethylthiourea
6 mmol were sequentially added, and once the temperature was raised to 70 ° C. and then lowered again to 50 ° C., and silver chlorobromide fine particles (Br 60 mol%,
(Containing potassium hexachloroiridate (IV)) 1.
6. 7 mmol, silver chlorobromide fine particles (Br 30 mol%)
1 mmol, 1- (3-methylureidophenyl) -5
-Mercaptotetrazole 0.2 mmol, 1-phenyl-5-mercaptotetrazole 0.2 mmol, KB
The red-sensitive emulsion R1 was prepared by sequentially adding 1.5 mmol of r. Emulsion R1 was a high silver chloride cubic emulsion having a side length of 0.41 μm, a coefficient of variation in grain size of 0.09, and a Br content of 0.66 mol%.

[0067]

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(3 × 10 ⁻⁵ mol per mol of silver halide per red-sensitive emulsion R1 and 3.5 × 10 ⁻⁵ mol per mol of silver halide per red-sensitive emulsion R1 ′) .)

This emulsion R1 was processed in the same manner as in Table 3 except that the amount of potassium hexachloroiridate (IV) in the silver chlorobromide fine particles and the variation coefficient of the particle size were changed as shown in Table 3. Emulsions R2 to R4 were prepared. Also,
The following emulsion R1 'was prepared by changing the temperature of the solution I and the addition rate of the solutions II to V to the emulsion R1, and changing the amount of chemicals added after adjusting the pAg. That is, emulsion R
1 ′ is a side length of 0.34 μm and a variation coefficient of particle size of 0.0
8. A high silver chloride cubic emulsion having a Br content of 0.80 mol%. This emulsion R1 'was treated in the same manner as in Example 3 except that the amount of potassium hexachloroiridate (IV) in the silver chlorobromide fine particles, the particle size, and the coefficient of variation of the particle size were changed as shown in Table 3. Emulsions R2 'to R4' were prepared. Grain size of each emulsion, coefficient of variation of grain size,
Table 3 shows the iridium content.

[0070]

[Table 3]

To the red-sensitive emulsion R1, the temperature of the solution I and the addition speed of the solutions II to V were changed, the amount of potassium hexacyanoferrate (II) in the solution V was changed, and the chemicals added after pAg was adjusted. And the amount of potassium hexachloroiridate (IV) in the silver chlorobromide fine particles was changed, and instead of the red sensitizing dye G, the blue sensitizing dye A, B, C or the green sensitizing dye D was used. , E and F were added to prepare blue-sensitive emulsions B1 and B1 'and green-sensitive emulsions G1 and G1'.

[0072]

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(The blue-sensitizing sensitizing dyes A, B and C were added per mol of silver halide to the large-size emulsion B1 respectively.
2.2 × 10 ⁻⁴ mol, 3 × 10 ⁻⁵ mol, 1.8 × 10 ⁻⁴
2.5 × for the mole and small size emulsion B1 ′, respectively.
^10-4 mol, 3.4 x ^10-5 mol and 2.1 x ^10-4 mol were used. )

[0074]

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(Green photosensitive sensitizing dyes D, E, and F were added in an amount of 3.0 × 10 ^-4 mol and 6.0 × 10 ^-5 mol, respectively, to large-sized emulsion G1 per mol of silver halide. , 1.0 × 1
0 ^-5 mol, respectively 3.7 × to the small size emulsion G1 '
10 ^-4 mol, 7.4 x 10 ^-5 mol, and 1.2 x 10 ^-5 mol were used. )

Preparation of Samples (101) to (108) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. A sample (101) was prepared by applying a photographic constituent layer. K-1 and K-2 were added at 3 mg / m ² , 12
mg / m ² and 14% by mass of titanium oxide.

[0077]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
Shows the silver equivalent coating amount. First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion B1 having an average grain size of 0.71 μm and small-size emulsion B1 ′ having an average grain size of 0.62 μm (silver molar ratio)). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively. 0.28 mol% and 0.33 mol% of silver bromide were added to each size of emulsion, and a part of the surface of the silver chloride-based grain. 0.25 Gelatin 1.35 Yellow coupler (ExY-1) 0.41 Yellow coupler (ExY-2) 0.21 Color image stabilizer (Cpd-1) 0.08 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.95 Color mixture prevention agent (Cpd-4) 0.12 Color image stabilizer (Cpd-6) 0.007 Color image stabilizer (Cpd-7) 0.14 Color image stabilizer (Cpd-13) 0.006 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion G1 having an average grain size of 0.42 μm and small-size emulsion G1 ′ having an average grain size of 0.33 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. 0.12 Gelatin 1.20 Magenta coupler (ExM-1) 0.10 Magenta coupler (ExM-2) 0.05 Ultraviolet absorber (UV-1) 0.05 Ultraviolet absorber (UV-2) 0.02 UV absorber (UV-3) 0.02 UV absorber (UV-4) 0.03 Color image stabilizer (Cpd-2) 0.005 Color image stabilizer (Cpd-4) ) 0.002 Color image stabilizer (Cpd-7) 0 0.08 Color image stabilizer (Cpd-8) 0.015 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Color image stabilizer (Cpd-13) 0.004 Solvent (Solv-3) 0.10 Solvent (Solv-4) 0.19 Solvent (Solv-5) 0.17

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-6) 0.005 Color image stabilizer (Cpd-7) 0.10 Color image stabilizer (Cpd-13) 0.004 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 6: 4 mixture of large-sized emulsion R1 having an average grain size of 0.41 μm and small-sized emulsion R1 ′ of 0.34 μm (silver mole) The coefficient of variation of the particle size distribution is 0.09 and 0.08, respectively.) 0.18 Gelatin 1.00 Cyan coupler (ExC-1) 0.05 Cyan coupler (ExC-2) 0.18 Cyan coupler (ExC-3) 0.024 UV absorber (UV-1) 0.04 UV absorber (UV-3) 0.01 UV absorber (UV-4) 0.01 Color image stabilizer (Cpd-1) 0.23 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-12) 0.01 Color image stabilizer (Cpd-13) 0.006 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.34 Ultraviolet absorbing agent (UV-1) 0.08 Ultraviolet absorbing agent (UV-2) 0.03 Ultraviolet absorbing agent (UV-3) 0.03 Ultraviolet absorbing Agent (UV-4) 0.02 Ultraviolet absorber (UV-5) 0.01 Ultraviolet absorber (UV-6) 0.03 Solvent (Solv-7) 0.10 Seventh layer (protective layer) Gelatin 1. 00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-14) 0.01 Surfactant (Cpd-15) 0.01

[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0092]

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Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two0.2 mg / m^Two, 0.6 mg / m^Two, 0.
1mg / m^TwoWas added so that Blue-sensitive emulsion
Layer and the green-sensitive emulsion layer.
Chill-1,3,3a, 7-tetrazaindene,
Per mole of silver halide^-FourMole, 2 × 10
^-FourMole was added. Also, methacrylic acid was added to the red-sensitive emulsion layer.
Copolymer of butyl acrylate (mass ratio 1: 1, average molecular weight
Amount of 200,000 to 400,000) to 0.05 g / m^TwoTo
Was added. The second, fourth and sixth layers have
-3,5-disulfonate disodium each in 6
mg / m^Two, 6mg / m^Two, 18mg / m^TwoSo that
Was added. Also, to prevent irradiation, use emulsion
Add the following dyes to the layer
Was.

[0094]

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Further, Ab-1, Ab-2, Ab-
3 and Ab-4 in a total amount of 15.0 mg / m ² ,
60.0 mg / m ² , 5.0 mg / m ² and 10.0 mg
/ M ² .

[0096]

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As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

Samples (102) to (108) were prepared in the same manner as sample (101) except that the red-sensitive emulsion of the fifth layer was changed as shown in Table 4.

[0099]

[Table 4]

The following exposure and processing were performed on the sample (101). Through a red filter, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, color temperature of light source 3200)
K) to obtain an exposure amount of 250 lux · sec (lx · sec).
c) After the sensitometric gradation exposure with an exposure time of 10 ^-1 second, the following treatment was further performed.

Processing Step Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 45 ml Bleaching and fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 15 seconds-rinse (2) 38.0 ° C. 15 sec - rinse (3) ** 38.0 ℃ 15 seconds - rinse (4) ** 38.0 ℃ 20 sec 121 ml * photosensitive material 1 m ² per replenishment amount ** Fuji Photo Film Co., Ltd. rinse cleaning system Install RC50D in rinse (3), take out the rinse liquid from rinse (3), and send it to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 3g 26.3g Water was added to add 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml ammonium ethylenediaminetetraacetate (III) ammonium 47.0 g 94.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse liquid] [Tank liquid] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

By measuring the color density of the processed sample (101), sensitometry corresponding to the red-sensitive cyan color-forming layer was performed to obtain a characteristic curve. In the obtained characteristic curve, the exposure required to obtain the density of the unexposed portion + 0.02 is read, and the color density (D1) obtained when the exposure is performed at an exposure 10 times the exposure is obtained. I asked. In addition, a photometer (HIE type, manufactured by Fuji Photo Film Co., Ltd.) was applied to the sample (101) through a red filter.
Was used to give a sensitometric gradation exposure at an exposure time of 10 ^-4 seconds, and then the above-described processing was performed. By measuring the color density of the processed sample (101), sensitometry of 10 ^-4 seconds exposure corresponding to the red-sensitive cyan color-forming layer was performed to obtain a characteristic curve. From the obtained characteristic curve, the color density (D1 ′) was determined in the same manner as described above. In addition, in the characteristic curve of the 10 ^-4 second exposure, the density of the unexposed portion +
The exposure (E1) required to obtain a density of 0.02 was determined. Further, the exposure amount (E2) required to obtain a density 0.92 times the maximum color density in the characteristic curve of the above-mentioned 10 ^-1 second exposure in the characteristic curve of the 10 ^-4 second exposure was obtained. The HIE type sensitometer is a sensitometer designed to obtain a strong light source illuminance so that a required exposure amount can be obtained in a short time.

A woman wearing a red dress was photographed using NEXIAH400 (a negative film manufactured by Fuji Photo Film Co., Ltd.), and then the film was processed to obtain a negative image. Using SUPER FA-238 (Minilab manufactured by Fuji Photo Film Co., Ltd.), the samples (101) to (108) were subjected to post-exposure treatment through the obtained negative to obtain a color print image by surface exposure. Also, FRONT
IER350 (Digital minilab manufactured by Fuji Photo Film Co., Ltd., 10 ^-7 seconds per pixel, blue light 40 μW, green light 30
(0 μW, output of about 2 mW of red light), the obtained negative information is digitized, the output of the laser beam is modulated based on this information, and the samples (101) to (108) are scanned and exposed, and then processed. Thus, a color print image by scanning exposure was obtained. The difference in performance between the normal surface exposure and the scanning exposure, which is high-illuminance short-time exposure, was evaluated using the values of D1 '/ D1 and log (E2 / E1) and the image created by the method described above.

The color print images obtained by subjecting the samples (101) to (108) to surface exposure were all good.
From Table 5, samples (101) to (104) and (108)
The image obtained by scanning exposure is insufficient in the reproducibility of the shading of the red dress, whereas D1 ′ / D1 and log
It is clear that the images obtained by scanning and exposing the samples (105) to (107) in which the value of (E2 / E1) is within the range specified in the present invention have good reproducibility of the shadow of the red dress. .

[0108]

[Table 5]

Example 2 For each of the red-sensitive emulsions R3 and R3 ', the potassium hexacyanoferrate (II) in the solution V was removed, and the amounts of chloroauric acid and triethylthiourea added were changed. Red-sensitive emulsions R5 and R5
5 ′ was prepared. Also, red light-sensitive emulsions R6 and R6 'were prepared in the same manner except that 0.03 mmol and 0.05 mmol of potassium hexacyanoferrate (II) were added to solution V to red light-sensitive emulsions R5 and R5', respectively. did. In order to evaluate the production stability of the red-sensitive emulsions R5, R5 ', R6 and R6', each emulsion was prepared three times. Table 6
The preparation numbers are shown as # 1 to # 3. For the sample (101), as shown in Table 6, the red-sensitive emulsion used was
Samples (201) to (206) were prepared in the same manner except that 5, R5 ′, R6 and R6 ′ were used instead. The same evaluation as in Example 1 was performed for the samples (201) to (206).

As in Example 1, the samples of the present invention (201) to
All of the color print images obtained by surface exposure of (206) were good, and the reproducibility of the shade of the red dress in the image obtained by scanning exposure was also good. In contrast to the samples (201) to (203) in which only one kind of Group VIII metal complex of the periodic table is contained in the red photosensitive emulsion, the samples containing two kinds of Group VIII metal complex of the periodic table in the red photosensitive emulsion ( 20
As can be seen from the results in Table 6, 4) to (206) are repeated in the production of the emulsion, and it is clear that more stable performance can be obtained.

In this embodiment, when an image was obtained by scanning exposure, when samples (201) to (203) were used,
In order to match the color of the finished image, it was necessary to correct the gradation for each sample using the calibration function installed in the digital minilab, whereas for samples (204) to (206) In this case, it is only necessary to perform calibration once for any of the samples.
4) to (206) Samples (204) to (206) were obtained because satisfactory images were obtained for all the samples.
Is more preferable in terms of productivity.

[0112]

[Table 6]

[0113]

The silver halide color light-sensitive material of the present invention has the excellent effects of rapid processing, excellent shading in the high-density portion of an image in scanning exposure, and high-quality color photography by surface exposure. .

Claims (3)

[Claims] 1. A halogen having at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler and a red-sensitive silver halide emulsion layer containing a cyan coupler on a support. A silver halide color photographic light-sensitive material, wherein at least one of the light-sensitive silver halide emulsion layers contains an emulsion having silver halide grains having a silver chloride content of 95 mol% or more, and A silver halide color photographic light-sensitive material characterized by satisfying the following relationships with respect to each characteristic curve obtained by color development. 0.65 ≦ D1 ′ / D1 ≦ 0.85 1.1 ≦ log (E2 / E1) ≦ 1.4 D1: In the characteristic curve obtained by exposing at an exposure time of 10 ⁻¹ sec, the density of the unexposed portion + 0 Density obtained when exposure is performed at an exposure amount that is 10 times the exposure amount required to obtain a density of 2.02. D1 ': Density of an unexposed portion in a characteristic curve obtained by exposure at an exposure time of 10 ^-4 seconds. Density obtained when exposure is performed at an exposure amount 10 times the exposure amount required to obtain a density of +0.02 E1: density of an unexposed portion in a characteristic curve obtained by exposure at an exposure time of 10 ^-4 seconds Exposure amount required to obtain a density of +0.02 E2: In the characteristic curve obtained by exposing at an exposure time of 10 ^-4 seconds, the maximum density 0 in the characteristic curve obtained by exposing at an exposure time of 10 ^-1 second Exposure required to obtain .92 times the density 2. The silver halide color photographic light-sensitive material according to claim 1, wherein a characteristic curve obtained by subjecting the light-sensitive material to color development after exposure to red light satisfies the above relationship. 3. The emulsion according to claim 1, wherein the emulsion contains silver halide grains having a silver chloride content of at least 95 mol% and containing at least two kinds of Group VIII metal complexes of the periodic table.
Or the silver halide color photographic light-sensitive material according to item 2.