JPH09304890A - Color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming method by which no irregular image is produced, decrease in the max. color developing density is suppressed and the max. color density does not variate by overlapped width of rasters when a photosensitive material is exposed by scanning with a light beam to form an image. SOLUTION: A silver halide color photographic sensitive material having at least one silver halide emulsion layer on a supporting body is exposed by scanning with light beams which are modulated based on the image information and then developed to form an image. In this method, silver halide particles in the silver halide emulsion is composed of silver chloride or silver chloride bromide which contains >=90mol% silver chloride and does not substantially contain silver iodide. The emulsion contains at least one kind of group VIII metal in the periodic table by 10<-9> to 10<-2> mol per one mol of the silver halide. More than >=50mol% of the whole amt. of the metal is included in the surface layer (phase) which is <=45% of the silver halide particle volume. This silver halide color photographic sensitive material is exposed by scanning with a light beam whose scanning pitch is smaller than the effective beam diameter and the overlapped width of rasters is >=5% and <=95% of the effective beam diameter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for scanning and exposing a silver halide color photographic light-sensitive material with a light beam to form an image, and more particularly to a color image forming method for scanning and exposing with a light beam modulated by a computer. Regarding

[0002]

2. Description of the Related Art With the development of computer technology in recent years, it has become possible to process an image read by a scanner on a computer screen (image processing) and create an image intended by the user relatively easily. When making a hard copy of this image, a digital exposure apparatus equipped with a semiconductor laser, a light emitting diode, or the like is often employed. Since the digital exposure device can scan and expose a photosensitive material in a short time and with high illuminance, it is characterized in that the exposure speed can be increased and the resolution can be improved. In response to the demand for higher image quality, studies have been made on the use of silver halide photographic light-sensitive materials, and image formation by a digital scanning exposure method has been performed. Various image forming methods based on the scanning exposure method have been conventionally known. For example, Japanese Patent Publication No. 62-21305 discloses a method of subjecting a photographic light-sensitive material to scanning exposure using a light emitting diode as a light source. Japanese Patent Application Laid-Open No. 62-35352 discloses scanning exposure of a high silver chloride photographic material with a laser beam. JP-A-63-18346 discloses a scanning exposure method using a second harmonic obtained by using a semiconductor laser and an SHG element as a light source.

In the case of exposing a photosensitive material by scanning and exposing a light beam generated from the light emitting diode or the semiconductor laser, the light beam is generally scanned by a raster scanning method. According to such an exposure method, a silver halide photographic light-sensitive material can be digitally exposed to obtain a full-color image. Furthermore, with the development of laser diodes in recent years, a simple and stable laser output device can be manufactured, and an image forming system using the laser output device is being put to practical use. For example, U.S. Pat. No. 4,619,8
No. 92 or No. 4,956,702 discloses the use of a silver halide photographic light-sensitive material having a maximum sensitivity in the infrared region as a light-sensitive material for output from a laser diode. On the other hand, silver halide photographic light-sensitive materials have recently become applicable to the field of recording digital information due to the development of high silver chloride emulsion technology. As such a technique, for example, International Publication WO87 / 04
In No. 534, the total image forming time is shortened by using high silver chloride as the silver halide of the light-sensitive material.

However, when images are formed by these methods, variations in density between rasters are emphasized due to lot-to-lot differences in photosensitive material, temperature conditions during exposure, and processing variations after exposure, resulting in image unevenness. Is likely to occur. It is known that these problems can be ameliorated by the overlap between rasters in scanning exposure.
Japanese Patent Application Laid-Open No. 4-249244 discloses a method for eliminating image unevenness by setting the overlap between rasters to 15% to 95% of the beam diameter. Further, in Japanese Patent Laid-Open No. 19423/1993, there is disclosed a method for improving the exposure temperature dependency using a silver halide photographic light-sensitive material having a high silver chloride emulsion, in which the overlap between rasters is set to 5% to 95% of the beam diameter. It is disclosed.
However, in these methods, a problem caused by the fact that the scanning exposure is short-time exposure of high-illuminance light (deterioration of photographic property in high-illuminance exposure of silver halide), specifically, scanning exposure (particularly 1 It has been found that the maximum color density (Dmax) is reduced by 1 × 10 ⁻⁶ seconds or less per pixel) and the maximum color density (Dmax) is changed due to the overlapping width between rasters, which is not practical.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce image unevenness and to suppress a decrease in maximum color density when an image is formed by scanning exposure of a photosensitive material with a light beam. It is an object of the present invention to provide a color image forming method in which the maximum color density does not change depending on the overlapping width between rasters.

[0006]

As a result of intensive studies by the present inventors, the above object was effectively achieved by the color image forming methods described in (1) to (3) below. (1) At least one silver halide emulsion layer is formed on a support.
In an image forming method in which a silver halide color photographic light-sensitive material having a layer is subjected to scanning exposure with a light beam modulated based on image information and then development processing, the silver halide grains in the silver halide emulsion have a silver chloride content of 90 mol. % Or more of silver chloride or silver chlorobromide, and contains 10 ^-9 to 10 ^-2 mol of at least one Group VIII metal of the periodic table per mol of silver halide, and the total content thereof In a silver halide color photographic light-sensitive material having a surface layer (phase) of which 50 mol% or more of the above is contained in 45% or less of the volume of the silver halide grain, the scanning pitch by the light beam is smaller than the effective beam diameter, and the raster A method for forming a color image, characterized in that scanning exposure is performed such that an overlapping width thereof is 5% or more and 95% or less of an effective beam diameter. (2) The silver halide color photographic light-sensitive material has at least one layer selected from a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. Is a visible light beam, and the color image forming method according to item (1). (3) The color image forming method as described in (1) or (2) above, wherein the silver halide grains are sensitized with gold.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION First, scanning exposure will be described. The scanning exposure applied in the present invention is a scanning exposure in which the overlapping width between rasters (light beam trajectories) is 5% to 95% of the effective beam diameter, and the overlapping width between rasters is preferable in order to prevent image unevenness. Is 15% to 85%, most preferably 20%
~ 80%. Here, the effective beam diameter is as described in
It is determined by the same method as described in the lower left of page 4 of 19423. That is, 50% of the laser light intensity sufficient to give the highest color density in the image to be formed to the light-sensitive material.
One line segment is exposed using a laser beam of the output of, and color development processing is performed to obtain a linear color image. The density profile of this color image is measured in the vertical direction of the line using a microdensitometer. The line width of the density D1 / 5 corresponding to 1/5 of the maximum density Dmax of this profile is defined as the effective beam diameter. The effective beam diameter in scanning exposure can be determined from the pixel density of the target output image, but the pixel density preferable as a pictorial image is generally in the range of 50 dpi to 2000 dpi. Converting this to pixel size, it is about 10-500
μm. The effective beam diameter preferably used in the present invention is 5 to 200 μm, and more preferably 10 to 100 μm.
μm. The scanning pitch in the present invention is defined by a raster interval, and when a light beam is a circle, it is expressed by an interval between beam centers. In the present invention, the effective beam diameter needs to be larger than the image scanning pitch.
Specifically, the overlapping width between rasters is in the relation of the following mathematical formula. L: overlapping width between rasters, d: effective beam diameter, p: scanning pitch L = d−p From the above formula, the scanning pitch applied in the present invention is preferably 0.25 μm to 190 μm, and 2 μm to 80 μm.
μm is most preferred. In light beam scanning, a photosensitive material is wrapped around a cylindrical drum, which is rotated at high speed to perform main scanning, and the light source is gradually moved in the axial direction of the cylinder to perform sub-scanning, so-called drum scanning. However, it is also possible to perform the main scanning by making the light beam incident on a polyhedral mirror surface (polygon mirror) that rotates at high speed, and the sub-scanning by moving the photosensitive material in a direction perpendicular to this. Is more preferable. The number of surfaces of the polygon mirror is not particularly limited, but is preferably 2 to 36, and particularly preferably 6 to 14. The stable rotation speed of the polygon mirror is preferably in the range of 4000 to 36000 rpm. By multiplying the number of rotations by the number of mirror surfaces, the number of scanning lines per time can be calculated. As means for generating a light beam, various known light sources can be used.
The present invention has a remarkable effect when a high illuminance light source such as a semiconductor laser, a gas laser and a light emitting diode is used.
Further, a semiconductor laser is used to make the system more compact and inexpensive, or a second harmonic generation light source (a semiconductor laser or a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal combined) is used. It is preferred to use (SHG). Particularly, in order to design a device that is compact, inexpensive, has a long life, and has high stability, it is preferable to use a semiconductor laser. The wavelength of the light beam in the present invention can be arbitrarily set according to the spectral maximum of the photosensitive material. Further, the exposure time per pixel in the present invention is preferably 10 ⁻⁴ seconds or less,
0 ^-6 seconds or less is more preferable.

When the above-mentioned scanning exposure light source is used, the spectral sensitivity maximum of the light-sensitive material of the present invention can be set by the wavelength of the scanning exposure light source used. It is particularly preferable that the spectral sensitivity maximum of the light-sensitive material of the present invention is in the visible region of blue, green, and red in view of handleability of the light-sensitive material and commonality with general light-sensitive materials. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material is normal blue, green,
It is possible to have it in the three red areas. In order to use a semiconductor laser as a light source that can make the device inexpensive, highly stable, and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because the available inexpensive and stable periodic table III and V semiconductor lasers currently only have emission wavelengths in the red to infrared region. However, at the laboratory level, oscillations of the Group II and VI semiconductor lasers of the periodic table in the green and blue regions have been confirmed, and if semiconductor laser manufacturing technology develops, these semiconductor lasers can be used stably at low cost. It is fully anticipated that this could be done. In such a case, at least two layers are 67
The need to have a spectral sensitivity maximum above 0 nm is reduced.

In the present invention, the silver halide emulsion used in the light-sensitive emulsion layer is substantially free of silver iodide and suitable for rapid processing. Silver chloride having a silver chloride content of 90 mol% or more or chloroodor. A high silver chloride emulsion made of silver halide is used. The phrase "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2% or less. In the present invention, the silver chloride content of the high silver chloride emulsion is 9
It is preferably 5 mol% or more, more preferably 98 mol% or more. The silver halide grains of the present invention include a Group VIII metal of the periodic table, that is, osmium, iridium, rhodium, platinum,
Ions of metals selected from ruthenium, palladium, cobalt, nickel and iron or complex ions thereof can be used alone or in combination. The amount of these metal ions used is preferably 10 per mol of silver halide.
It is in the range of ^-7 to 10 ^-3 mol. These metal ions will be described in more detail, but not limited to these.

The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, of which the complex salt is preferred.
For example, primary iridium (III) chloride, primary iridium (III) bromide, secondary iridium (IV) chloride, sodium hexachloroiridium (III), potassium hexachloroiridium (IV), hexaammineiridium (IV)
Salts, trioxalatoiridium (III) salts, trioxalatoiridium (IV) salts, and other complex salts having halogens, amines, or oxalic acid as a ligand are preferable. The platinum ion-containing compound is a divalent or tetravalent salt or complex salt, of which a complex salt is preferable. For example, chloroplatinic (IV) acid, potassium hexachloroplatinum (IV), potassium tetrachloroplatinum (II), sodium tetrabromoplatinum (II), tetrakis (thiocyanato) platinum (IV), hexaammineplatinum (IV) ) Chloride or the like is used.

The palladium ion-containing compound is usually a divalent or tetravalent salt or complex salt, and a complex salt is particularly preferable. For example, sodium tetrachloropalladium (II), sodium tetrachloropalladium (IV), potassium hexachloropalladium (IV), tetraamminepalladium (II) chloride, tetracyanopalladium (II)
Potassium acid or the like is used. As the nickel ion-containing compound, for example, nickel chloride, nickel bromide, potassium tetrachloronickel (II) acid, hexaammine nickel (II) chloride, sodium tetracyanonickel (II) acid or the like is used.

The rhodium ion-containing compound is usually preferably a trivalent salt or complex salt. For example, potassium hexachlororhodate, sodium hexabromorhodate, ammonium hexachlororhodate, etc. are used. The iron ion-containing compound is a divalent or trivalent iron ion-containing compound, and is preferably an iron salt or iron complex salt having water solubility in the concentration range used. Particularly preferred is an iron complex salt which can be easily contained in silver halide grains. For example ferrous chloride,
Ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous thiocyanate, ferric thiocyanate, iron hexacyano (II)
There are complex salts, hexacyanoiron (III) complex salts, ferrous thiocyanate complex salts, ferric thiocyanate complex salts, and the like. Further, a six-coordinate metal complex having at least four cyan ligands as described in European Patent EP 0,336,426A is also preferably used.

The above-mentioned metal ion-providing compound is added to a gelatin aqueous solution, a halide aqueous solution, a silver salt aqueous solution, or any other aqueous solution which becomes a dispersion medium at the time of silver halide grain formation, or a metal ion is added in advance. It can be incorporated in the silver halide grains of the present invention by a means such as adding to the silver halide emulsion in the form of contained fine silver halide grains and dissolving the fine grains. Also,
The group VIII metal ion used in the present invention can be contained in the particles before, during, or after the formation of particles. It can be changed depending on which position and in which amount of the composition.

In a preferred embodiment of the present invention, 50 mol% or more (preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 100 mol%) of the metal ion-providing compound used is silver halide. Surface layer (phase) from the particle surface to the equivalent of 45% or less of the particle volume
It is preferably localized at. The volume of this surface layer (phase) is preferably 30% or less, more preferably 20%.
% Or less. Surface layer (phase) in which this metal ion is localized
When the volume is as small as possible (thin), it is advantageous to suppress an increase in internal sensitivity and obtain high sensitivity. In order to concentrate the metal ion-providing compound in the surface layer (phase) of such a silver halide grain, for example, after forming the silver halide grain (core) in a portion excluding the surface layer (phase), the surface layer (phase) is formed. It can be carried out by supplying the metal ion-providing compound in accordance with the addition of the water-soluble silver salt solution and the aqueous halide solution for forming the (phase).

A silver bromide-rich phase is preferably imparted to the silver halide grain of the present invention. The silver bromide-rich phase of the silver halide grain of the present invention is near the apex of the grain. It is preferable that at least 10 mol% or more of the total silver bromide content in the localized phase is epitaxially grown. In the present invention, the term “near the vertex” preferably refers to a projected cube or a salt (odor) of a normal crystal similar to a cube.
The length of one side of the diameter of a circle having the same area as the area of the silver halide particle, more preferably 1/5, is defined as one side, and the vertex of the particle (intersection of the cubic or the ridge of the normal crystal grain regarded as a cubic)
Within the area of a square whose one corner is. The total silver bromide content of the silver bromide rich layer 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 layer is preferably in the range of 10 to 60 mol%, and most preferably in the range of 20 to 50 mol%. The silver bromide content of the localized phase having a high silver bromide content is determined by using an X-ray diffraction method (for example, described in “New Experimental Chemistry Account 6, Structural Analysis” Maruzen, edited by The Chemical Society of Japan). Can be analyzed. The silver bromide-rich layer is preferably composed of 0.1 to 5 mol% of the total silver constituting the silver halide grains of the present invention, and is composed of 0.3 to 4 mol% of silver. It is more preferable that

As is generally well known, the steps of preparing a silver halide emulsion in the present invention include a step of forming a silver halide grain by a reaction of a water-soluble silver salt and a water-soluble halide, a desalting step and a chemical ripening step. Consists of. The application of the silver bromide-rich phase in the present invention is preferably prior to the chemical ripening step, more preferably prior to the desalting step, particularly after the formation of the silver halide host grains. It is preferable to be performed. It is preferable to incorporate a metal group VIII metal complex ion such as IrCl ₆ ²⁻ into the silver bromide-rich phase of the present invention. 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 silver bromide 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. Further, after mixing silver halide fine particles having a smaller average particle size than the silver halide host particles and a high silver bromide content,
When forming a silver bromide-rich phase by aging,
It is preferable to preliminarily contain an iridium salt in the silver halide fine particles having a high silver bromide content.

The silver halide grains used in the present invention may have a (100) face, a (111) face, or both faces on the outer surface. Alternatively, a cube having a higher order plane may be included, but a cube mainly composed of (100) planes,
Alternatively, a tetrahedron is preferred. The size of the silver halide grains of the present invention may be within the range usually used,
It is preferable that the average particle size is 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 preferably 0.2 or less, more preferably 0.15 or less, in the ratio (s / d) of the standard deviation (s) and the average particle size (d) in statistics. preferable. It is also preferable to use a mixture of two or more monodisperse emulsions.

The shape of silver halide grains is cubic or 14
Regular other than octahedron as well as octahedron
Those having a crystal form, those having an irregular crystal form such as a sphere, a plate, or the like, or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to the grains having a regular crystal form, tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, have a projected area of 50% by weight or more of all grains. Emulsions can also be preferably used. The silver chlorobromide emulsion used in the present invention is P.Gl
Chimie et Phisique Photographique (Paul by afkides
Montel, 1967), GF Duffin, Photographic E
mulsion Chemistry (Focal Press, 1966), VLZ
Making and Coating Photographic Em by elikman et al
ulsion (Focal Press, Inc., 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 halogen salt may be a one-side mixing method, a simultaneous mixing method, or a combination thereof. May be used. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of simultaneous mixing method,
It is also possible to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion used in the present invention is
In addition to the Group VIII metals by Ming, the formation of emulsion grains
Various polyvalent metal ion impurities in the process of physical ripening
Can be introduced. Examples of compounds used
Is a salt of cadmium, zinc, lead, copper, thallium, etc.
Or a complex salt can be used in combination. These compounds
Depending on the purpose, the amount of addition of a wide range of
10 to 1 mol of silver halide ^-9-10^-2Molar is preferred. Book
The silver halide emulsion used in the invention is usually chemically sensitized and separated.
Photosensitized. Unstable sulfur for chemical sensitization
Represented by sulfur sensitization, represented by the addition of compounds, gold sensitization
Noble metal sensitization or reduction sensitization
Can be used. Compounds used for chemical sensitization
No. 18 of JP-A No. 62-215272.
Those described in the lower right column of the page to the upper right column of page 22 are preferably used.
Can be

The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like can be further reduced. 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 from 5 × 10 ^{-7 to} 5 × 10 ^-3 mol, preferably 1 × 1 ^-7 mol per mol of silver halide.
It is 0 ^-6 to 1 × 10 ^-4 mol.

In the present invention, gold sensitization is performed by another sensitization method,
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.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in the wavelength range corresponding to the desired spectral sensitivity. As the spectral sensitizing dye used at this time, for example, FM Harmer “Heterocy
clic compounds-Cyanine dyes and related compounds ''
(John Wiley & Sons New York, published by London, 1964). Examples of specific compounds and the spectral sensitization method are disclosed in JP-A-62-215272.
Those described in the right upper column of page 22 to page 38 of the publication are preferably used.

The silver halide emulsion used in the present invention contains various compounds or precursors thereof for the purpose of preventing fog during production process of the light-sensitive material, storage or photographic processing or stabilizing photographic performance. It can be added. Specific examples of these compounds are disclosed in JP-A-62-21527.
Those described on pages 39 to 72 of Japanese Patent Publication No. 2 are preferably used. The emulsion used in the present invention is preferably a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer can be decolorized by photographic treatment described in pages 27 to 76 of European Patent EP 0,337,490A2 for the purpose of improving sharpness of an image. A dye (among others, an oxonol dye) can be added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.50 or more.

In the present invention, instead of the water-soluble dye or in combination with the water-soluble dye, a colored layer which can be decolorized by treatment is used. The colored layer that can be decolorized by the treatment may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below the emulsion layer (on the side of the support) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. Regarding the optical reflection density of the colored layer, it is preferable that the optical density value at the wavelength having the highest optical density also in the wavelength of the light source color used for scanning exposure is 0.2 or more and 3.0 or less. It is more preferably 0.5 or more and 2.5 or more, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, dyes described in JP-A-2-282244, page 3, right upper column to page 8, and dyes described in JP-A-3-282244,
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, and a dye Examples thereof include a method of adsorbing to fine particles such as silver halide and fixing it in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-30
8244, pp. 4-13. Further, for example, a method of mordanting an anionic dye with a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. A method for preparing colloidal silver as a light absorber is shown in US Pat. Nos. 2,688,601 and 3,459,563. Among these methods, a method of incorporating a fine powder dye, a method of using colloidal silver, and the like are preferable.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, it is preferable to use a low calcium gelatin having a calcium content of 800 ppm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a mold preventive agent as described in JP-A-63-271247. The exposed light-sensitive material may be subjected to a conventional color development treatment, but in the case of the light-sensitive material of the present invention, it is preferable to perform bleach-fixing treatment after color development for the purpose of rapid processing. In particular, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material of the present invention, and the processing method applied for processing the light-sensitive material and As processing additives, the following Table 1
Patent publications shown in Table 5, especially European Patent No. 0,355,66
Those described in the specification of 0A2 (JP-A-2-139544) are preferably used.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

Cyan, magenta or yellow couplers are impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents listed in the table above, Alternatively, it is preferably dissolved with a water-insoluble polymer soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and WO 88/00723 at pages 12 to 30. The homopolymers or copolymers mentioned may be mentioned. More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferred in view of color image stability and the like.

In the light-sensitive material of the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler.
In particular, combination use with a pyrazoloazole coupler, a pyrrolotriazole coupler, or an acylacetamide type yellow coupler is preferable. That is, the compound and / or the color development treatment in the above-mentioned European Patent Specification which chemically bonds with an aromatic amine-based developing agent remaining after the color development treatment to form a chemically inactive and substantially colorless compound. After chemically bonding with the oxidant of the aromatic amine color developing agent that remains afterwards,
It is possible to use the compounds in the above-mentioned European patent specification, which form a chemically inert and substantially colorless compound, simultaneously or alone, for example, with the residual color developing agent in the film during storage after processing or its oxidant. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the coupler.

Further, as a cyan coupler, JP-A-2-
No. 33144, a diphenylimidazole type cyan coupler, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0,333,185A2, and a cyclic active methylene type cyanine described in JP-A-64-32260. Coupler, European Patent EP 0,45
6,226A1 specification, pyrrolopyrazole-type cyan coupler, European Patent EP 0,484,909, pyrroloimidazole-type cyan coupler, European Patent E
P0,488,248 and EP0,491,1
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Among them, use of a pyrrolotriazole type cyan coupler is particularly preferred.

Examples of magenta couplers include 5-pyrazolone type magenta couplers as described in the known documents in the above table. Examples of 5-pyrazolone-based magenta couplers include WO 92/18901,
The arylthio-eliminating 5-pyrazolone-based magenta couplers described in O92 / 18902 and WO92 / 18903 are preferable in terms of image storability and little change in image quality due to processing. Known pyrazoloazole couplers are used in the present invention. Among them, secondary or tertiary alkyl groups as described in JP-A-61-65246 in view of hue, image stability, color developability and the like. Is directly linked to the 2, 3 or 6 position of the pyrazoloazole ring, a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in Kaishoku 61-147254 and European Patent No. 226,849A.
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in JP-A No. 294,785A.

As the yellow coupler, known acylacetanilide type couplers are preferably used. Among them, a pivaloylacetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring, European Patent No. 0,447, No. 969A, JP-A-5-1077
No. 01, 5-113642 and the like.
Acylacetanilide type couplers which are substituted cycloacylcarbonyl groups, EP 0,482,552A
No. 0,524,540A, etc., and the malondianilide type couplers described therein are preferably used. In the present invention, a yellow color-forming silver halide emulsion layer on a support,
A color light-sensitive material can be constructed by coating at least one of a magenta color forming silver halide emulsion layer and a cyan color forming silver halide emulsion layer. In a general color photographic paper, since a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed is formed, color reproduction by the subtractive method can be performed by incorporating a coupler. In general color photographic paper, silver halide emulsion grains are spectrally sensitized by blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dyes in the order of the above-described color-forming layers, respectively, and on a support in the order described above. It can be formed by coating. However, the order may be different. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so.

The support used in the present invention is glass, paper,
Any support can be used as long as it can be coated with a photographic emulsion layer such as a plastic film, but the most preferred is a reflective support. The "reflective support" that can be used in the present invention refers to one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear, and such a reflective support may be formed on the support. Examples include those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support.
For example, polyethylene-coated paper, polyester (for example, polyethylene terephthalate) -coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or together with a reflective substance, such as a glass plate, polyethylene terephthalate, cellulose triacetate, or nitric acid. Examples include polyester films such as cellulose, polyamide films, polycarbonate films, polystyrene films, and vinyl chloride resins. The reflective support used in the present invention is a paper support whose both surfaces are coated with a water resistant resin layer, and it is preferable that at least one of the water resistant resin layers contains white pigment fine particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflecting white pigment particles, it is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces are treated with a dihydric or tetrahydric alcohol. It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of particles, and the size of the distribution is determined by the occupation area ratio (%) (Ri) of the fine particles projected on a unit area. It can be determined by measuring. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, more preferably 0.12 or less. 0.0
Particularly preferred is 8 or less.

The support of the present invention may contain an optical brightener, if necessary. The optical brightening agent used is a benzoxazolylnaphthalene or benzoxazolyl stilbene type optical brightening agent. The amount used is selected depending on the required performance, but is 0.0005 to 0.35%, and more preferably 0.001 to 0.10% with respect to the resin such as polyolefin.

In the present invention, a support having a surface of diffuse reflection of the second kind may be used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the second-class diffuse reflective surface has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. The frequency of surface irregularities is 0.1 to 200 for irregularities with a roughness of 0.1 μm or more.
0 cycle / mm is preferable, and further 50-
It is preferably 600 cycles / mm. Details of such a support are described in JP-A-2-239244.

As the processing method of the light-sensitive material of the present invention, in addition to the methods described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-Hei. No. 4-97355, page 5, upper left column, line 7 to page 18, lower right column 20,
The processing material and processing method described in the line are also preferable. Also,
It is also preferable to incorporate a developing agent into the photosensitive material and develop with an activator solution such as an alkali solution containing no developing agent.

As a wet developing method for a light-sensitive material, a method using an ordinary developing solution or an activator solution is available. In particular, the activator treatment method is a preferred method from the viewpoint of environmental preservation because the processing solution does not contain a color developing agent, so that the treatment solution can be easily managed and handled, and the load of waste liquid treatment is small. In the activator processing method, a light-sensitive material containing a color developing agent or its precursor is used. For example, Japanese Patent Application Nos. 7-63572 and 7-334190,
7-334192, 7-334197, 7-
A light-sensitive material containing a hydrazine type compound as a color developing agent described in JP-A-344396 is preferable. In addition, a low-silver photosensitive material is used for image amplification (intensification processing) using hydrogen peroxide.
The method described in Japanese Patent Application No. 7-63 is also preferably used.
The image forming method using an activator solution containing hydrogen peroxide described in JP-A No. 582 and JP-A No. 7-334202 is preferably used.

After the activator processing, desilvering processing is usually carried out. However, in the image amplification processing using a light-sensitive material having a low silver content, desilvering processing is unnecessary, and simple washing processing or stabilizing processing after the activator processing is required. preferable. Further, in a method in which image information is read by a scanner or the like as a photographing material, a processing form that does not require desilvering processing is possible even when a high silver content photosensitive material is used.

Regarding the processing materials and methods of the activator solution, desilvering solution, washing and stabilizing solution used in the present invention,
For details, see Japanese Patent Application No. 7-63572, Research Disclosure Item 36544 (September 1994) 5.
Pp. 36-541.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto. Example 1 (Preparation of emulsion B-101) 32.0 g of lime-processed gelatin
Was added to 1000 cc of distilled water, dissolved at 40 ° C., adjusted to pH 3.8 with sulfuric acid, 5.5 g of sodium chloride and N, N′-dimethylimidazolidine-2-thione 0.0
2g was added and the temperature was raised to 52.5 ° C. Subsequently, a solution prepared by dissolving 5.0 g of silver nitrate in 140 cc of distilled water and a solution prepared by dissolving 1.7 g of sodium chloride in 140 cc of distilled water were added and mixed at 52.5 ° C. with vigorous stirring. Next, 120 g of silver nitrate was dissolved in 320 cc of distilled water and 41.3 g of sodium chloride was added to 320 cc of distilled water.
While stirring vigorously with the liquid dissolved in cc, 52.5 ° C
And mixed. After desalting and washing with water at 40 ° C,
76.0 g of lime-processed gelatin was added, and pAg was adjusted to 7.9 and pH was adjusted to 6.2 with sodium chloride and sodium hydroxide. After the temperature was raised to 50 ° C., the following blue-sensitive sensitizing dyes A and B were added in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver halide, and triethylthiourea was used to optimize sulfur content. I sensitized. The silver chloride emulsion thus obtained was designated as Emulsion B-101.

(Preparation of Emulsion B-102) Emulsion B-101
Means 5 × 10 ⁻⁵ mol of K ₃ per mol of silver halide
A silver chloride emulsion was prepared in which an aqueous solution containing Fe (CN) ₆ was added only at a rate that always kept a constant ratio with the concentration of silver nitrate added from the start of the addition of the aqueous silver nitrate solution to the end thereof. Was designated as Emulsion B-102. (Preparation of Emulsion B-103) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
_A silver chloride emulsion was prepared in which the aqueous solution containing ₆ was added only from the start of the addition of the aqueous silver nitrate solution to the time when 50% of the total amount of silver nitrate was added at a rate that always kept a constant ratio with the concentration of silver nitrate added. This emulsion was designated as Emulsion B-103. (Preparation of Emulsion B-104) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
_A silver chloride emulsion was prepared in which the aqueous solution containing ₆ was added only after 20% of the total amount of silver nitrate was added and until the end of the addition of silver nitrate, at a rate that always maintained a constant ratio with the concentration of silver nitrate added. This emulsion was designated as Emulsion B-104. (Preparation of Emulsion B-105) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
_A silver chloride emulsion was prepared in which an aqueous solution containing ₆ was added only after 50% of the total amount of silver nitrate had been added and until the end of the addition of silver nitrate, at a rate that kept a constant ratio with the concentration of silver nitrate added. This emulsion was designated as Emulsion B-105. (Preparation of emulsion B-106) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
_A silver chloride emulsion was prepared which differs only in that the aqueous solution containing ₆ was added at a rate that maintains a constant ratio with the concentration of silver nitrate added until 55% of the total amount of silver nitrate has been added until the end of the addition of silver nitrate. This emulsion was designated as Emulsion B-106. (Preparation of Emulsion B-107) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
An aqueous solution containing ₆ was added to 70% of the total amount of silver nitrate, and until the end of the addition of silver nitrate, a silver chloride emulsion was prepared which differed only in the addition concentration of silver nitrate at a constant rate. This emulsion was designated as Emulsion B-107. (Preparation of Emulsion B-108) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
An aqueous solution containing ₆ was added to 80% of the total amount of silver nitrate, and until the end of the addition of silver nitrate, a silver chloride emulsion was prepared which was different from the concentration of silver nitrate added only at a constant rate. This emulsion was designated as Emulsion B-108. (Preparation of Emulsion B-109) Emulsion B-101 means 5 × 10 ⁻⁵ mol of K ₃ Fe (CN) per mol of silver halide.
An aqueous solution containing ₆ was added to 90% of the total amount of silver nitrate, and until the end of the addition of silver nitrate, a silver chloride emulsion was prepared which differed only in the addition concentration of silver nitrate at a rate that kept a constant ratio. This emulsion was designated as Emulsion B-109. (Preparation of Emulsion B-110 to Emulsion B-111) Emulsion B-1
08-Emulsion B-109, when subjected to spectral sensitization and chemical sensitization, a monodisperse silver bromide emulsion having an average grain size of 0.05 μm (1.2 × 10 ⁻⁵ mol per mol of silver bromide) was used. Emulsion B-110 to Emulsion B-111 were obtained by adding 0.5 mol% of iridium (IV) hexachloride (containing dipotassium hexachloride) as silver halide. (Preparation of Emulsion B-112 to Emulsion B-113) Emulsion B-1
07 to Emulsion B-108, silver chloride emulsions were prepared which differed only in that gold sensitization was optimally performed with chloroauric acid instead of sulfur sensitization, and these emulsions were designated as Emulsion B-112 to Emulsion B-.
It was set to 113.

Emulsion B-101 thus prepared
The grain shape, grain size, and coefficient of variation of the 13 types of emulsions B to B-113 were determined from electron micrographs.
The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the coefficient of variation used was a value obtained by dividing the standard deviation of the particle size by the average particle size. Emulsions B-101 to B-11
The 13 types of emulsions of No. 3 all had a grain size of 0.46μ.
It was a monodisperse cubic particle having m and a coefficient of variation of 0.09.

[0049]

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Emulsions B-101 to Emulsion B-113 were prepared in the same manner as Emulsion G-101 except that they were spectrally sensitized with the following green light-sensitive spectral sensitizing dyes C and D.
To Emulsion G-113. Furthermore, Emulsion B-101 to
Emulsions B-113 to Emulsion R-113 were emulsions that differed only in that they were spectrally sensitized with the following red-sensitive spectral sensitizing dyes.

[0051]

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[0052]

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The following compounds were added to the red-sensitive emulsion in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0054]

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For the purpose of preventing irradiation, the following dyes were added to the emulsion layer.

[0056]

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After the corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form the layers shown below. A multilayer color photographic paper (101) having the constitution was produced. The coating solution was prepared as follows. Preparation of First Layer Coating Solution 122.0 g of yellow coupler (ExY), 15.4 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.7 g are dissolved in solvent (Solv-1) 44 g and ethyl acetate 180 cc, and this solution contains 10% sodium dodecylbenzenesulfonate 86 cc and citric acid 10 g. An emulsified dispersion was prepared by emulsifying and dispersing in 1000 g of 10% gelatin aqueous solution. This emulsified dispersion and the above emulsion B-101 were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the second to seventh layers are also applied to the first layer.
It was prepared in the same manner as the liquid. As a gelatin hardener for each layer
1-oxy-3,5-dichloro-s-triazine
Thorium salt was used. In addition, Cpd-12 and Cp are added to each layer.
d-13, Cpd-14 and Cpd-15 all
Amount is 15.0mg / m^Two, 60.0 mg / m^Two, 5.0 mg / m^TwoOver
And 10.0 mg / m^TwoWas added. Also blue sensitive
1-layer emulsion layer, green photosensitive emulsion, red photosensitive emulsion layer
(5-Methylureidophenyl) -5-mercaptotet
3.3 × for each mole of silver halide
10^-FourMole, 1.0 × 10^-3Moles and 5.9 x 10^-FourMo
Added. Further, the second layer, the fourth layer, the sixth layer, and the
0.2 mg / m for each of the seven layers^Two, 0.2 mg / m^Two, 0.6
mg / m^Two, 0.1 mg / m^TwoWas added. Again blue feeling
4-hydroxy-6- for the photosensitive emulsion layer and the green-sensitive emulsion layer
Methyl-1,3,3a, 7-tetrazaindene
1 x 10 per mole of silver halide ^-FourMole and 2 × 10
^-FourMole was added.

(Constituent Layer) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive emulsion layer) Said silver chloride emulsion B-101 0.24 Gelatin 1 .33 Yellow coupler (Ex-Y) 0.61 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent ( Solv-1) 0.22

Second layer (color mixing prevention layer) Gelatin 1.09 Color mixing inhibitor (Cpd-4) 0.11 Color image stabilizer (Cpd-16) 0.15 Solvent (Solv-1) 0.07 Solvent (Solv -2) 0.25 solvent (Solv-7) 0.01

Third Layer (Green Sensitive Emulsion Layer) The Silver Chloride Emulsion G-101 0.11 Gelatin 1.19 Magenta Coupler (Ex-M) 0.12 UV Absorber (UV-1) 0.12 Color Image Stability Agent (Cpd-2) 0.01 Color image stabilizer (Cpd-4) 0.01 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer ( Cpd-8) 0.01 Color image stabilizer (Cpd-16) 0.08 Color image stabilizer (Cpd-18) 0.0001 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.20 Solvent (Solv-5) 0.11 Solvent (Solv-9) 0.19

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.77 Color mixing inhibitor (Cpd-4) 0.08 Color image stabilizer (Cpd-16) 0.11 Solvent (Solv-1) 0.05 Solvent (Solv -2) 0.18 Solvent (Solv-7) 0.01 Fifth layer (red sensitive emulsion layer) Said silver chloride emulsion R-101 0.18 Gelatin 0.80 Cyan coupler (Ex-C) 0.28 UV absorption Agent (UV-3) 0.19 Color image stabilizer (Cpd-1) 0.24 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer ( Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.21

Sixth Layer (UV Absorbing Layer) Gelatin 0.64 UV Absorber (UV-2) 0.39 Color Image Stabilizer (Cpd-7) 0.05 Color Image Stabilizer (Cpd-17) 0.05 Solvent (Solv-8) 0.05 Seventh layer (protective layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01

[0064]

[Chemical 6]

[0065]

[Chemical 7]

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

[Chemical 12]

[0071]

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Based on the light-sensitive material (Sample 101) obtained as described above, light-sensitive materials in which the emulsions were replaced as shown in Table 1 were prepared, and Samples 102 to 113 were prepared.

[0073]

[Table 6]

These samples were subjected to scanning exposure with the following visible light beam, and changes in the maximum color density (Dmax) due to overlap between rasters were examined. As a light source, a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm)
YAG solid state laser (oscillation wavelength, 94
6 nm) was wavelength-converted by an SHG crystal of KNbO ₃ and was extracted at 473 nm, and a semiconductor laser GaAlAs was used.
(Oscillation wavelength, 808.7 nm) as excitation light source
₄ Solid-state laser (oscillation wavelength, 1064 nm) wavelength converted by SHG KTP crystal and extracted 532 nm
And AlGaInP (oscillation wavelength, about 670 nm: Toshiba type No. TOLD9211). The laser light of each of the three colors is moved in a direction perpendicular to the scanning direction by a polygon mirror, so that the laser light can be sequentially scanned and exposed on color printing paper. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. First, the effective beam diameter of each laser beam in these samples was measured. According to the method described above, after linearly exposing the sample using each laser, color development was performed with the processing steps and processing solutions shown below, and the reflection density of the obtained image was measured by a microdensitometer. Then, the effective beam diameter (d) was obtained. The results are shown in Table 2. Further, Table 3 shows the ratio of the overlapping width (L) between rasters at each scanning pitch with the effective beam diameter.

The composition of each processing liquid is as follows. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 10 liters Bleach fixing 35 ℃ 45 seconds 218ml 10 liters Rinse (1) 35 ℃ 30 seconds -5liters Rinse (2) 35 ℃ 30 seconds -5 Liter rinse (3) 35 ℃ 30 seconds 360ml 5 liter Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material (3 tank countercurrent system from rinse (3) to (1))

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid 0.5 g 0.5 g Disodium salt Triethanolamine 12.0 g 12.0 g Potassium chloride 2.5 g-Odor Potassium iodide 0.01 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical) 1.0 g 2.5 g Sodium sulfite 0.1 g 0.2 g Disodium-N, N-bis (sulfonate ethyl) 5.0 g 8.0 g Hydroxylamine N-ethyl-N- (β-methanesulfonamidoethyl) 5.0 g 7.1 g-3-Methyl-4-aminoaniline / 3/2 sulfuric acid / monohydrate Water was added to 1000 ml 1000 ml pH (25 ° C. / With potassium hydroxide and sulfuric acid) 10.05 10.45

Bleach-fixing solution (tank solution and replenisher are the same) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid (III) ammonium 55 g Ethylenediaminetetraacetate iron 5 g Ammonium bromide 40 g Sulfuric acid (67%) 30 g Water added 1000 ml pH (25 ° C / acetic acid and ammonia water) 5.8 Rinse solution (same as tank solution and replenisher) Sodium chlorinated isocyanurate 0.02 g Deionized water Conductivity 5μS / cm or less) 1000 ml pH 6.5

[0078]

[Table 7]

[0079]

[Table 8]

The exposure amount of each sample was controlled by an external modulator, and gradation exposure was applied. At this time, the scanning pitch is 84.7 μm (300 dpi), 63.5 μm (400
dpi) and 42.3 μm (600 dpi). The average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds.

The color development processing of each exposed sample was the same as that for obtaining the effective beam diameter.
Yellow, magenta, and yellow of each of the samples 101 to 113 after the treatment.
The maximum color density (Dmax) of cyan was measured. The results are summarized in Table 4.

[0082]

[Table 9]

Fe ions are not present in the particles (Sample 1
01), Fe ions are uniformly present in the particles (Sample 1)
02), Fe ions inside the particles (50% inside the particle volume)
Up to) (Sample 103) or Fe ions are present from 20% to 100% (surface) of the inside of the particle volume (Sample 104), the maximum color density is low.
The maximum color density increased as the scanning pitch was decreased. Even if Fe ions are present only in the surface layer of the particles, they are present in 50% of the volume of the particles from the surface layer (Sample 1).
In the case of 05), the maximum color density was decreased, and the maximum color density was increased as the scanning pitch was decreased. However, in the case where the Fe ions of the present invention are present only in the surface layer of 45% or less of the particle volume (Sample 106 to Sample 111), the maximum color density is high and stable even when the scanning pitch is changed. . In addition, gold sensitized emulsion (Sample 112, Sample 1
13) also had the same effect.

Example 2 32.0 g of lime-processed gelatin was added to 1000 cc of distilled water, dissolved at 40 ° C., adjusted to pH 3.8 with sulfuric acid, 5.5 g of sodium chloride and N, N′-dimethylimidazo. Lysine-2-thione 0.02 g was added and the temperature was adjusted to 6
Raised to 6 ° C. Subsequently, 5.0 g of silver nitrate was added to 1 part of distilled water.
While stirring vigorously, a solution dissolved in 40 cc and a solution prepared by dissolving 1.7 g of sodium chloride in 140 cc of distilled water were vigorously stirred.
The above liquid was added and mixed at 6 ° C. Next, silver nitrate 90.0g
Solution of distilled water in 228 cc of distilled water and sodium chloride 3
A solution prepared by dissolving 1.0 g of distilled water in 228 cc was added and mixed at 66 ° C. with vigorous stirring. Further silver nitrate 25.
A liquid in which 0 g was dissolved in 92 cc of distilled water and a liquid in which 8.6 g of sodium chloride was dissolved in 92 cc of distilled water were added and mixed at 66 ° C. with vigorous stirring. After desalting and washing with water at 40 ° C., 76.0 g of lime-processed gelatin was added,
Further, the pAg was adjusted to 7.9 and the pH was adjusted to 6.2 with sodium chloride and sodium hydroxide. After the temperature was raised to 50 ° C., the spectral sensitizing dyes A and B used in Example 1 were respectively added to 2.0 × 10 ⁻⁴ mol per mol of silver halide and further monodispersed bromide having an average grain size of 0.05 μm. The silver emulsion was added as silver halide in an amount of 0.5 mol%, and optimally sulfur-sensitized with triethylurea. The obtained silver chloride emulsion was designated as Emulsion B-201.

Emulsion B-201 was prepared by adding an aqueous solution containing the compounds shown in Table 5 at the same time as the addition of the silver nitrate aqueous solution and the sodium chloride aqueous solution which are added for the third time.
Silver chloride emulsions were prepared which differed only by the fact that the silver bromide-rich phase contained 1.2 × 10 ^-5 mol of dipotassium hexachloroiridate (IV) per mol of silver bromide, and these were prepared as emulsion B-20.
2 to Emulsion B-210.

[0086]

[Table 10]

In the method for preparing the emulsions of emulsion B-201 to emulsion B-210, emulsions having an average grain size of 0.46 μm were prepared by changing the temperature during the formation of silver halide emulsion grains and the addition rate of the reaction solution. Example 1 with a spectral sensitizing dye
The green light-sensitive spectral sensitizing dyes C and D used in Example 1 were replaced with Emulsion G-201 to Emulsion G-210.

In the emulsion preparation of Emulsion G-201 to Emulsion G-210, the average grain size was adjusted to 0.5 by changing the temperature during the formation of silver halide emulsion grains and the addition rate of the reaction solution.
An emulsion of 3 μm was prepared, and spectral sensitization was carried out in the same manner as in Example 1 using the red light-sensitive spectral sensitizing dye of Example 1 to give Emulsion R.
-201 to Emulsion R-210. Among these emulsions, Emulsion B-209, Emulsion G-209, Emulsion R-209
As a result of halogen composition analysis by X-ray diffractometry for the three types, a main peak of 100 mol% of silver chloride and a sub-peak corresponding to a silver bromide content of 30 to 40% were observed. It was confirmed that the emulsion grains had a silver bromide-rich phase. Using the emulsions thus obtained, multi-layer coating was carried out with combinations of the emulsions shown in Table 6 to prepare 10 types of color light-sensitive materials. Example 1
Was performed in the same manner as described above.

[0089]

[Table 11]

The same test as in Example 1 was conducted using the 10 kinds of coated samples thus obtained. This result is the seventh
Shown in the table.

[0091]

[Table 12]

As is clear from the results, Fe and Fe
The effect of the present invention was remarkable also in the other Group VIII metals of the periodic table.

Example 3 The same test as in Example 1 was conducted using the support coated with the optical brightening agent shown in Table 8 below. As a result, the same results as in Example 1 were obtained regardless of the support.

[0094]

[Table 13]

The optical brighteners (K) and (L) are shown below.

[0096]

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[0097]

According to the present invention, the maximum color density (Dmax)
It is possible to obtain a color image forming method in which the maximum color density does not fluctuate due to the overlapping width between rasters, while suppressing the deterioration of the image quality. The present invention is particularly suitable for exposing a photosensitive material for a short time with a high-illuminance light source such as a semiconductor laser, a gas laser, and a light emitting diode.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/00 G03C 7/407 1/035 B41J 3/00 D 1/09 B 7/00 520 3 / 21 L 7/407

Claims (3)

[Claims] 1. An image forming method in which a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support is scanned and exposed by a light beam modulated based on image information and then developed. The silver halide grains in the silver halide emulsion are substantially silver iodide-free silver chloride or silver chlorobromide having a silver chloride content of 90 mol% or more, and more than 10 ^-9 per mol of silver halide. 10 ^-2
Halogen containing at least one metal of Group VIII metal in the periodic table, and 50 mol% or more of the total content of which is 45% or less of the volume of the silver halide grains in the surface layer (phase). A color characterized by subjecting a silver halide color photographic light-sensitive material to scanning exposure in which the scanning pitch by the light beam is smaller than the effective beam diameter and the overlapping width between rasters is 5% or more and 95% or less of the effective beam diameter. Image forming method. 2. The silver halide color photographic light-sensitive material has at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, The color image forming method according to claim 1, wherein the light beam is a visible light beam. 3. The color image forming method according to claim 1, wherein the silver halide grains are gold-sensitized.