WO2004068239A1

WO2004068239A1 - Image forming method

Info

Publication number: WO2004068239A1
Application number: PCT/JP2003/000988
Authority: WO
Inventors: Toyoki Nishijima
Original assignee: Konica Corporation
Priority date: 2003-01-31
Filing date: 2003-01-31
Publication date: 2004-08-12

Abstract

An image forming method for forming a stable image excellent in sharpness with no variation in density in the image part even after continuous printing by means of a high-speed digital printer. The method in which a silver halide color photosensitive material that includes blue, green, and red photosensitive layers containing silver halide and formed on a support is scanned for exposure with a light beam for an exposure time of 1×10-3 second or less per pixel and subjected to color development is characterized in that the maximum exposure (Emax) for image forming is adjusted by the output of a calibration patch, the difference Δlog E between the logarithm of the exposure (E0.3) at which the reflection density of the silver halide color photosensitive material is 0.3 and the logarithm of Emax is 0.35 to 0.6 for the blue, green, and red photosensitive layers, and at least one of the color image forming layers contains silver halide chemically sensitized by a selenium compound.

Description

Image forming method Technical field

The present invention relates to an image forming method using a silver halide color photographic light-sensitive material, in which the density fluctuation in a high-speed digital print and the gradation fluctuation in a multiple exposure are improved and excellent in sharpness. Background art

In recent years, the number of opportunities for handling images as digital data has been rapidly increasing in accordance with the improvement in the computing power of computers and network technology. Image information captured by a digital camera or image information that has been converted into digital data from a film or print using a scanner, etc., can be edited and processed on a computer, and data such as character first can be added. Can be done relatively easily. Hard copy materials for producing hard copies based on such digitized image information include, for example, sublimation type thermal transfer prints, fusion type thermal transfer prints, ink jet prints, electrostatic transfer type prints, Photochromic materials and silver halide color photographic light-sensitive materials can be mentioned. Among them, silver halide color photographic light-sensitive materials (hereinafter, also referred to as color prints or light-sensitive materials) are high. It has excellent properties compared to other print materials, such as sensitivity, excellent gradation, excellent image preservation, and low cost. Especially today for creating high quality hard copy It has been.

Image information that has been converted into digital data using a scanner or the like can be edited and processed on a computer, or data such as character diasts can be added relatively easily.For example, people, landscapes, still life, etc. There is an increasing number of opportunities to handle images that contain both images (such as “scene images”) based on photographic data and character images (especially thin, small black character images). Therefore, in image output based on digital data, it is necessary to simultaneously satisfy the two requirements of reproducing scene images more naturally and character images without blurring.

In order to reproduce digitized image data as a silver halide photograph, it is necessary to perform exposure while changing the exposure amount according to the image data. At this time, it is known that a calibration operation is performed so that the density of the image reproduced on the print based on the image data matches the target density. Conventionally, if the calibration operation is performed with a focus on natural reproduction of the scene image (particularly color reproduction and detail reproduction from the middle density area to the high density area), blurring of the character image tends to occur. Carrying out the rebalancing operation, paying attention to the fact that the character image is less likely to bleed, makes the reproduction of the scene image more likely to be unnatural. In order to achieve both reproduction, it was necessary to repeat the calibration operation by trial and error while changing the exposure conditions little by little, and improvements were desired.

In order to solve the above problem, a method has been disclosed in which the maximum gamma and the fill-in Dmax at the time of digital exposure are specified to improve the sharpness in a high-density region so that the blur of a character image does not easily occur. For example, see Patent Document 1), when a density exceeding the fill-in Dmax is reproduced, the character quality is greatly degraded. It does not describe the natural reproduction of the image. Also, a technique for improving the character quality by defining a dynamic range and an N value (degree of bleeding) in the magenta image forming layer is disclosed (for example, see Patent Document 2).

The color balance of the outline of a character image in a high density range exceeding 2.0 tends to be lost, and improvement thereof has been desired.

Also, many digital image exposure apparatuses are currently being sold, and a number of new digital image exposure apparatuses are being researched and developed along with advances in exposure light sources and control devices. Among these digital image exposure apparatuses, apparatuses using sharp light source wavelength distributions such as lasers and LEDs as exposure light sources are becoming mainstream. However, the types of lasers and LEDs mounted on various digital image exposure apparatuses are not uniform, and the exposure wavelength often differs for each exposure apparatus. While beautiful prints can be reproduced, different exposure systems with different exposure wavelengths tend to cause bleeding in the high-density region and unnatural scene image reproduction. I got it.

In digital scanning exposure, gradation degradation due to reciprocity failure characteristics in short-time exposure of a silver halide color photographic light-sensitive material is likely to occur. Generally, as a method of improving the reciprocity failure characteristic of a silver halide photographic material, a high illuminance such as a laser can be obtained by adjusting the amount of a doped metal, for example, iridium, in a silver halide emulsion. It is known that high gradation can be obtained by short-time exposure. However, when a large amount of prints are output over a long period of time using a laser exposure device, the output is due to differences in the exposure model and changes in the light source suitability of the laser exposure unit when printing large amounts. Fluctuates in the printed print (concentration variation) The problem that g) occurs has been identified, and urgent improvement is required.

(Patent Document 1)

JP-A-9-1171237 (Claims)

(Patent Document 2)

Japanese Patent Application Laid-Open No. 10-20461 (Claims) Disclosure of the Invention

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

(1) A blue-sensitive yellow image forming layer containing a photosensitive silver halide, a green photosensitive magenta image forming layer, and a red photosensitive cyan image forming layer each containing at least one layer on a support. An image forming method in which a silver halide color photographic light-sensitive material is subjected to scanning exposure with a light beam such that the exposure time per pixel is 10 to ³ seconds or less and then color development processing is performed. adjusts the maximum exposure amount at the time more image formed on the output of the patch (E _max), and said silver halide color - photographic light-sensitive material, a pair of exposure amount giving a reflection density 0. ₃ (E .. 3) The difference ΔL 0 g E between the numerical value and the logarithmic value of E _max is as follows in the blue-sensitive yellow-color image forming layer, the green-sensitive magenta image forming layer, and the red-sensitive cyan image forming layer, respectively. 0.35 or more, 0.6 or less and the number of color image forming layers is small. Both one layer, the image forming how, characterized in that it contains a silver halide that has been subjected to by Ri chemical sensitization selenium compound.

The horizontal axis is obtained by performing exposure and color development processing in (2) 10 ⁶ seconds or less exposure time: exposure (L o _g E), vertical axis: on the characteristic curve consisting of color density, density 0. The image forming method according to (1), wherein the variation of the average gradient of a straight line passing through the point giving 5 and the point giving density 1.5 is within 1 QQ / 6 in multiple exposure. (3) the silver halide color one photographic light-sensitive material, the exposure time is obtained by performing exposure and color development processing at 90 seconds and 10 one ⁶ seconds, the yellow color image (B), magenta color image (G ) And the density ratio (D _maxB / D _maxG , D _raaxR D _raaxG ) of each maximum density D _ma on the characteristic curves of the cyan image (R) are in the range of _{0.7 to} _1.3 , respectively. The image forming method according to (1) or (2). BEST MODE FOR CARRYING OUT THE INVENTION

The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a blue-sensitive yellow image forming layer containing a photosensitive silver halide, a green photosensitive magenta image forming layer, After subjecting a silver halide color photographic material having at least one photosensitive cyan image forming layer to scanning exposure with a light beam such that the exposure time per pixel is 10 to ³ seconds or less, In an image forming method for performing color development processing, the maximum exposure amount (E _max ) during image formation is adjusted by the output of a calibration patch, and the silver halide color photographic material has a reflection density of 0.3. and the logarithm of the exposure amount (E .. ₃₎ to give the difference delta L og E between the logarithmic value of the E _max is該青photosensitive I E port color image forming layer, green-sensitive magenta color image forming layer And 0.35 or less each for the red-sensitive cyan image forming layer , 0.6 or less, and at least one of the color image forming layers contains silver halide chemically sensitized with a selenium compound. It has been found that an image forming method in which density fluctuation (particularly, maximum density variation) and gradation fluctuation in multiple exposure can be improved can be realized, and the present invention has been reached.

In addition to the above configuration, Gyotsu exposure and color development processing in the following exposure time 1 0 ⁶ seconds Horizontal axis: exposure amount (L0gE), vertical axis: average slope of a straight line passing through a point giving density 0.5 and a point giving density 1.5 on the characteristic curve consisting of color density the variation of it is within 10% in the multiple exposure, or silver halide color one photograph photosensitive material, the exposure time is obtained by performing exposure and color development processing at 90 seconds and 10 ⁶ seconds, yellow color image (B), the concentration ratio of the maximum density D _max on the characteristic curve of the magenta image (G) and cyan Iroga image _{_{(R) (D maxB ZD maxG}} , D maxR ZD maxG) force, each 0.7 It has been found that the above effects can be further exhibited by being within the range of ~ 1.3.

Hereinafter, details of the present invention will be described.

According to the image forming method of the present invention, in the image forming method of performing a color developing process after performing a scanning exposure with a light beam such that an exposure time per pixel is 10 to ³ seconds or less, the output of the calibration patch The maximum exposure (時_max ) at the time of image formation is adjusted according to, and the logarithm of the exposure (Eo. ₃ ) which gives the silver halide color photographic light-sensitive material a reflection density of 0.3, The difference _{ΔLogE from} the logarithmic value of _max is 0.35 or more for the blue-sensitive yellow one-color image forming layer, the green-sensitive magenta color image-forming layer, and the red-sensitive cyan color image-forming layer. One feature is that it is less than 6. The logarithmic value in the present invention is a common logarithmic value with a base of 10. Usually, when image information is digitized and handled, it is common to divide the original image into small squares and digitize and handle the density information for each square. In the present invention, the minimum unit in the case where the original image is divided into squares and handled is one pixel. Therefore, the exposure time per pixel can be considered as the time during which the intensity or the irradiation time of the light beam is controlled based on the digital data for one pixel. . Scanning exposure with a light beam is usually performed by linear exposure with a light beam (raster exposure: main scanning) and relative movement (sub-scanning) of the photosensitive material in a direction perpendicular to the linear exposure direction. It is common to do this in combination. For example, a photosensitive material is fixed to the outer or inner circumference of a cylindrical drum, and the drum is rotated while irradiating a light beam to perform main scanning, and at the same time, the light source is moved perpendicular to the rotation direction of the drum. In this way, a sub-scanning method (drum method) is performed by irradiating a rotated polygon mirror with a light beam, and the reflected beam is scanned (horizontal scanning) horizontally with the rotation direction of the polygon mirror. A method of performing sub-scanning by transporting the polygon perpendicular to the rotation direction of the polygon (polygon method) is often used. In the case of using an exposure apparatus in which light sources are arranged in an array beyond the width of the photosensitive material to be exposed, it is possible to regard that a portion corresponding to main scanning is substituted by an array light source. Can be considered.

In the present invention, _{Era ax} refers to data representing the maximum density on image data when exposing based on digitized image data (for example, processed on Adobe's P hot 0 Sh 0 p For image data having 8-bit gradation, it is defined as the exposure amount when exposure is performed based on (R, G, B) = (0, 0, 0) is the image data representing the maximum density). You.

In addition, the E o. ₃ referred to in the present invention, stearyl one task A reflection density (R, G, B) and outputs the gray patches of the secondary (0.3 0, 0.3 0, 0.3 0) It is defined as the amount of exposure necessary for each color image forming layer.

E o. If the difference between the logarithm of the _third logarithm and E _max to zero. Greater than 6, the bleeding of the character image contour is likely to occur, also 0.3 in the case of less than 5, the digital dew Light control becomes difficult. Also, all yellow, magenta, and cyan image forming layers If the above conditions are not satisfied, the color blur is likely to occur in the outline of the character image.

In the image forming method of the present invention, the horizontal axis is obtained by performing exposure及beauty color development following the exposure time 10- ⁶ seconds: exposure (L 0 g E), vertical axis: or color density It is preferable that the variation of the average gradient of a straight line passing through the point giving the density of 0.5 and the point giving the density of 1.5 on the characteristic curve be within 10% in multiple exposure. The characteristic curve referred to in the present invention is that, after performing high illuminance exposure for 10 to ¹⁶ seconds or less, and performing an image obtained by performing a standard color development process, the horizontal axis represents Log E (E is the exposure amount), The vertical axis is the curve plotted with D (color density). Further, the multiple exposure, the time of the high intensity exposure below 10- ⁶ seconds, exposed to the same pixel more than once which means that pressurized Erareru. In addition, the variation of the average gradient at that time means that after performing one and two exposures, the characteristic curve obtained by color development passes through the points where density 0.5 and density 1.5 are given. It means the difference gradient (ta _n) when a straight line is drawn. Ideally, the fluctuation of the density gradient due to multiple exposure is a state where there is no fluctuation of the average gradient.

In the image forming method of the present invention, a silver halide color one photographic light-sensitive material, the exposure time is obtained by performing exposure and color development processing at 90 seconds and 10 ⁶ seconds, the yellow color image (B) , Magenta color image (G) and cyan color image (R) on each characteristic curve, the density ratio of each maximum density _Dmax ( _DmaxB / _DmaxG , D / D power, each in the range of _{0.7 to 1.3)} Is preferred.

That is, the maximum exposure amount (E _max ) during image formation is adjusted by the output of the calibration patch, and each of the yellow, magenta, and cyan image forming layers is exposed at the exposure amount E _max. Cyan image reflection density of black image area The ratio of (D _maxR ) to the magenta color image reflection density (D _maxG ) (Dma ZD xG) and the ratio of the yellow one-color image reflection density (D _maxB ) to (D _raaxG ) (D _maxB / D _raaxG ) are: Each is preferably from 0.7 to 1.3, more preferably from 0.8 to 1.2, and still more preferably from 0.9 to 1.2. The reflection density here indicates the status A reflection density.

The types of light sources that can be used in the image forming method of the present invention include a light emitting diode (LED), a gas laser, a semiconductor laser (LD), a solid laser using an LD or an LD as an excitation light source, and a second laser. Well-known, such as a combination with a harmonic change element (so-called SHG element), a combination of a tungsten light and a bandpass filter, a combination of a halogen lamp, a PLZT element and a color filter, a combination of a VF PH element and a color filter, etc. Any light source can be used. In particular, blue light sources with a wavelength of 400 to 450 nm are currently being vigorously researched and developed, mainly for high-density recording on optical discs such as digital video discs (DVDs). ing. As one of methods, for example, a semiconductor laser with an oscillation wavelength of 800 to 900 nm - (e.g., G a A s system) and the second harmonic generation (S HG) element (e.g., L i N b 0 ₃ system, L Inorganic crystals such as iTa03 series, organic crystals such as 2-methyl-14-nitroaniline), and oscillation wavelengths of 380 to 380 nm using InGaN-based materials. A blue semiconductor laser with a wavelength of 430 nm and a dye laser using a scintillator dye or a coumarin dye are known. Above all, the overlap with the spectral sensitivity distribution of the green photosensitive layer is slightly smaller for solid-state lasers in combination with SHG and for semiconductor lasers whose oscillation wavelength is 380 to 430 nm compared to 431 to 480 nm. Even if the blue light intensity on the recording material surface is increased, the green photosensitive layer This is a particularly preferable exposure light source in the present invention, because unnecessary color development can be reduced, and bleeding of a yellow image, which is considered to be caused by a decrease in light scattering in the support, can be reduced.

There is no particular limitation on means for achieving the requirements specified in the image forming method of the present invention. For example, for example, the characteristics of the photosensitive silver halide contained in the photosensitive material are appropriately controlled, Reproduction density on data that represents maximum density on digitized image data, by appropriately controlling the amount of neutral silver halide, coupler, or anti-irradiation dye, or by setting calibration The methods for appropriately controlling the target values can be used alone or in combination.

The composition of the silver halide emulsion used in the light-sensitive material according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide. However, in the case of silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide, the effect of the present invention is remarkable, which is preferable. From the viewpoint of rapid processing and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable. In the light-sensitive material according to the present invention, from the viewpoint of reducing softening of the characteristic curve in a high-density region in short-time exposure with high illuminance, silver halide having a high-concentration portion of silver bromide is used. Emulsions can also be preferably used. In this case, the portion containing a high concentration of silver bromide may be formed by epitaxy bonding to silver halide grains, a so-called core-shell emulsion, or simply a partial formation without forming a complete layer. There may be only regions having different compositions. Further, the composition may be changed continuously or discontinuously. The part where silver bromide is present in high concentration It is particularly preferred that the surface be the surface of silver gemide grains or the apex of crystal grains.

In the light-sensitive material according to the present invention, it is preferable to use silver halide grains containing heavy metal ions from the viewpoint of reducing softening caused by high-illuminance short-time scanning exposure. Heavy metal ions that can be used for such purposes include irons, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and other Group 8-10 metals, cadmium, zinc, mercury, etc. Group 1 and 2 transition metals, and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferred. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

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

In order for the heavy metal ions to be contained in the silver halide grains, the heavy metal compound is physically added before forming silver halide grains, during silver halide grains, after forming silver halide grains, or the like. What is necessary is just to add in arbitrary places in each process during ripening. In addition, the solution of the heavy metal compound can be continuously added over the whole or a part of the particle forming step.

When the heavy metal ion is added to the silver halide emulsion, the amount is more preferably 1 × 10 to ⁹ mol or more and 1 × 10 to ² mol or less, more preferably 1 × 10 to ² mol per mol of silver halide. X 10- ⁸ mol 5 X 10_ ⁵ moles or less is preferable.

In the light-sensitive material according to the present invention, any shape can be used for the silver halide grains. One preferable example is a cube having a (100) plane as a crystal surface. In addition, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and the "Journa Nore Obove" Photographic Science (J P h 0 t 0 gr. S ci.)

Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Further, particles having twin planes may be used.

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

The grain size of the silver halide grains according to the invention is not particularly limited, but is preferably 0.1 to 1.2 ^ m, more preferably 0.1 to 1.2 ^ m, in consideration of other photographic properties such as rapid processing and sensitivity. , 0.2-1.0 m.

This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform, the size distribution can represent this fairly accurately as a diameter or projected area o

The particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably. Is to add two or more monodisperse emulsions having a coefficient of variation of 0.15 or less to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation. Coefficient of variation = SZR

(Where S is the standard deviation of the particle size distribution and R is the average particle size.)

The particle size referred to here is the diameter of a spherical silver halide particle, or the diameter of a cubic or non-spherical particle when the projected image is converted into a circular image of the same area. Represent.

Various methods known in the art can be used as a device and method for preparing a silver halide emulsion.

The silver halide emulsion used in the light-sensitive material according to the present invention may be obtained by any of an acid method, a neutral method, and an ammonium method. The particles may be grown at one time or may be grown after seed particles have been made. The method for producing the seed particles and the method for growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by a simultaneous mixing method is preferable. Further, as one form of the simultaneous mixing method, a pAg control single-jet method described in JP-A-54-48521 can be used.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble haeganide salt from an addition device disposed in a reaction mother liquor described in JP-A Nos. 57-92523 and 57-92524, published in Germany Apparatus for continuously changing the concentration of water-soluble silver salt and water-soluble halide salt aqueous solution described in Patent No. 2,921,164, etc., and reaction outside the reactor described in JP-B-56-501776, etc. An apparatus may be used in which the mother liquor is taken out and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant. If necessary, a silver halide solvent such as polyester may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

In the silver halide color photographic light-sensitive material according to the present invention, at least one of the color image forming layers contains silver halide chemically sensitized with a selenium compound (hereinafter, also referred to as a selenium sensitizer). Containing is one feature.

As the selenium sensitizer that can be used in the present invention, particularly, an unstable selenium compound that can react with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Patent Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-125832, and 4-109240. And No. 414, 147, 250, etc.

Useful selenium sensitizers include colloid selenium metal, isoselenosocyanates (eg, aryliselenosinate), selenoureas (eg, N, N-dimethylselenourea, N, N, N ′). 1-Triethylselenourea, N, N, ', ー' Tetramethylselenourea, Ν, Ν, — '—Trimethyl-1N' 1-Heptafluoroselenourea, Ν, Ν '—Dimethyl-1-Ν, —' — Bis (carboxymethyl) selenourea, Ν, Ν, Ν'-trimethyl-1-N'-heptaful-l-propylcarbonylselenourea, Ν, Ν, Ν'-trimethyl-: NT-14-nitrophenyl selenourea, etc.) Selenoketones (for example, selenoacetone, selenoacetophenonone, etc.), selenoamides (for example, selenoacetamide, N, N-dimethylselenobenzamide, N, N-ethylethyl 4-) Chi le aminosulfonyl Selenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-13-selenobutyrate, etc.), and selenophosphates (eg, tri-p-tolylselenophosphate, Pentafluorene phenyldiphenylselenophosphate, etc., selenides (eg, dimethylselenide, tributylphosphineselenide, triphenylphosphineselenide, tri-P-triphenylphosphineselenide, pentafluorophenyl) Diphenylphosphinselenide, triphenylphosphineselenide, tripridylphosphineselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. U.S. Patent Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,466, 3,297,447, and 3 , 320, 069, 3,408,196, 3,408,197, 3,442,653, 3,420,670, 3,591,385 Patent Nos. 2,693,038, 2,093,209, JP-B-52-34491, 52-34492, 53-295, 57-22090, JP 59-180536, 59-185330, 59-181337, 59-187338, 59-192241, 60-150046, 60-151637, 61-246738, and JP-A-Heisei 3 — No. 4221, No. 3— 24537, No. 3— 111838, No. 3— 116132, No. 3— 148648, No. 3— 237450, No. 4-1 81638, No. 4— 25832, No. 4— 32831, 4-1 33043, 4-196059, 4-1109240, 4-140738, 4-1 140 7 339, 4-1 147 2,500, 4-1 843 31 4-1 902 0 25, 4-191 729, 4-1 503 No. 5, No. 5-1 1 1 3 8 5, No. 5-403 24, No. 5-243 32, No. 5-243 33, No. 5-310 3 1 57, No. 5- 3 0 6 2 6 8 and 6- 3 0 6 6 9 and 6- 2 7.5 7 3 and 6- 7 5 3 2 8 and 6- 1 7 5 2 5 9 and 6 — 208 1 84, 6—2 08 186, 6—3 1 7867, 7—9 2599, 7—9 8483, 7—1 044 15 No. 7-140 5 79, No. 7-3 01 8 79, No. 7- 30 1880, No. 8 1 1488 2, No. 9-197 6 60, No. 9 138475, 9-16-16841, 9-13-18475, 9-1899779, 10-106666, JP2001-3437 No. 21, UK Patent No. 255,846, and No. 861, 984, and the like, and the Journal of P hotographic Sciences 31, 158—1 by HE S pencer et al. 6 9 (1 9 83).

A preferable addition amount of the selenium sensitizer according to the present ^{invention, 1 X 1 0- 9 ~1 X} 1 0- 1 molar Z moles A g X, more preferably ^{1 X 1 0- 8 ~ 1 X} 1 0 mol / Mol A g X

In order to add the selenium sensitizer according to the present invention to a silver halide emulsion, a method generally used in the art for adding an additive to a photographic emulsion can be applied. For example, when the compound is a water-soluble compound, an aqueous solution having an appropriate concentration is used. When the compound is insoluble or hardly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, and ketones. Can be added as a solution by dissolving in a solvent that does not adversely affect the photographic properties such as alcohols, esters and amides. In the silver halide emulsion used in the light-sensitive material according to the present invention, a known chemical sensitization method, for example, a sensitization method using a gold compound, or a sensitization method using a chalcogen sensitizer is used together with the selenium sensitizer. Sensitization can be used. As the chalcogen sensitizer applied to the silver halide emulsion, an io sensitizer, a tellurium sensitizer and the like can be used, and an io sensitizer is preferable. Examples of the zeosensitizer include thiosulfate, trithiothiolbamidothiourea, T-lylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic zeolite. The addition amount of the sensitizer is preferably changed depending on the type of the silver halide emulsion to be applied and the size of the expected effect, but is preferably from 5 × ^{10 to 10} × 5 to 1 × ¹⁰ per mol of silver halide. ID- ⁵ mols, preferably 5 X 1 0 one ⁸ ~ 3 X 1 0- ⁵ mole range is preferred.

As a gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound to be used include dimethyl rhodanine, thiocyanate, mercaptotetrazol, and mercaptotriazole. The amount of the gold compound, the kind of silver halide emulsion, the type of compound used, but are not and ripening conditions, is usually 1 mol of silver halide per 1 X 1 0 one ⁴ mol ~ 1 X 1 It is preferably 0-1 ^s mole. More preferably, it is from 1 × 10 to ⁵ mol to 1 × 10 to ⁸ mol.

In the present invention, a silver halide emulsion can be optically spectrally sensitized to a desired wavelength region by adding a dye (spectral sensitizing dye) that absorbs light in a wavelength region corresponding to a target spectral sensitivity. The spectral sensitizing dye used at this time is, for example, FM Hamer Hetercycling—IC co mp ounds—C vaninedesandrelatedco mp ounds (John Wileyand Sons; New York, 1964). Examples of the spectral sensitizing dye used in the present invention include a cyanine dye, a merocyanine dye, and a complex merocyanine dye. In addition, there are complex cyanine dyes, horopora-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. As the cyanine dye, simple cyanine dye, carbocyanine dye, and dicarbocyanine dye are preferably used. The support that can be used in the present invention is preferably a paper support in which a resin coating layer is applied to both surfaces of a substrate.

As the paper support having a resin coating layer coated on both sides of the base paper, a paper support obtained by laminating both sides of the base paper with a polyolefin is preferable, and a paper support laminated with polyethylene is particularly preferable. is there.

The base paper used for the paper support is made of wood pulp as the main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fibers such as Nyopen® polyester in addition to wood pulp. . As wood pulp, any of LBKP, LB SP, NBKP, NB SP, LDP, NDP, LUKP, NUKP can be used, but L BKP, NB SP, LB SP, NDP, L It is preferred to use more DP. However, the ratio of LBSP and / or LDP is preferably from 10% by mass to 70% by mass.

As the pulp, a chemical pulp (sulfate / pulp or sulfite pulp) containing a small amount of impurities is preferably used, and a pulp having improved whiteness by a bleaching treatment is also useful. The base paper contains sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc, and titanium oxide; paper strength agents such as starch, polyacrylamide, and polyvinyl alcohol; and polyethylene glycol. A water-retaining agent such as water, a dispersant, a softening agent such as quaternary ammonium, and the like can be appropriately added. Further, the oil-soluble fluorescent whitening agent according to the present invention can also be used.

The freeness of the pulp used in papermaking is preferably 200 to 50 Om1 according to the CSF regulations, and the fiber length after beating is specified in JIS-P-8207. It is preferable that the sum of the mass and the mass% of the remaining 42 mesh is 30 to 70%. Preferably, the mass% of the four-mesh flower is 20% by mass or less. The basis weight of the base paper is preferably 30 to 250 g / m ² , particularly preferably 50 to 200 g / m ² . The thickness of the base paper is preferably from 40 to 250 m. The base paper can be calendered at the papermaking stage or after papermaking to provide high smoothness. The density of the base paper is generally 0.7 to 1.2 gZcm ³ (JIS-P-811). Further, the rigidity of the base paper is preferably 20 to 200 g under the conditions specified in JIS-P-8143. A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, the same sizing agent as that which can be added to the base paper can be used. The pH of the base paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS-P-8113.

The polyethylene that covers the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but some are also LLDPE (linear low-density-polyethylene) ゃ polypropylene, etc. Can be used. In particular, the polyethylene layer on the side of the photosensitive layer has improved opacity and whiteness by adding rutile or anatase type titanium oxide to polyethylene, as is widely practiced in photographic printing paper. preferable. The content of titanium oxide is usually 3 to 20% by mass relative to polyethylene, preferably 4 to 13% by mass.

Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melted and extruded onto the surface of a base paper to perform coating, a so-called molding process is performed to obtain a pine paper that can be obtained with ordinary photographic printing paper. A material having a textured surface-silk surface can also be used in the present invention.

The amount of each polyethylene used on the front and back of the base paper is usually in the range of 20 to 40 m for the polyethylene layer on the side where the photosensitive layer is provided and 10 to 30 m for the back layer side.

Further, the polyethylene-coated paper support preferably has the following properties.

1. Tensile strength:] "The strength specified by IS-P-8113, preferably 20 to 300 N in the vertical direction and 10 to 200 N in the horizontal direction.

2. Tear strength: According to the method specified in JIS-P-8116, it is preferable that the vertical direction is 0.1 to 20N and the horizontal direction is 2 to 2 ON.

3. Compression modulus ≥ 98. IMP a

4. Surface Beck Smoothness: Under the conditions specified in JIS-P-8119, 20 seconds or more is preferable for the glossy surface, but it may be less for so-called molded products.

5.Surface roughness: Surface roughness specified in JIS-B-0601, standard length 2.5 mm, maximum height is preferably 10〃m or less

6. Opacity: 80% or more, particularly preferably 85 to 98%, as measured by the method specified in JIS_P-8138

7. Whiteness: L *, a *, and b * specified by JIS—Z—8729 are L * = 80 to 95, a * = − 3 to 10, and b * = — 6 to 12, Preferably 8. Surface gloss: The 60-degree specular gloss specified in JIS-Z-8741 is preferably 10 to 95%

9. Clark stiffness: a support having a Clark stiffness of 50 to 300 cm10 in the recording medium transport direction is preferable.

10. Moisture content of middle paper: usually 2 to 100% by mass, preferably 2 to 6% by mass based on the middle paper

In the silver halide color photographic light-sensitive material of the present invention, constituent elements other than those described above, for example, other silver halide photographic emulsions, emulsion additives, sensitization methods, anti-fog agents, stabilizers, Anti-syllable dyes, yellow couplers, magenta couplers, cyan couplers, spectral dyes, emulsification dispersion method, surfactants, anti-turbidity agents, binders, hardeners, slip agents and matting agents, supports , Bluing agents and reddish agents, coating methods, color developing agents, processing methods, development processing equipment, processing agents, etc. are described in JP-A-1113-147615, p. No. 0044 to page 14, left column, line 17, paragraph No. 0106 can be used for each compound and method. Also, Research Disc Entrance Jar No. 1 7643, No. 18716 and No. 308 1 19 (hereinafter abbreviated as RD 1 7643, RD 18716 and RD 308 119, respectively) Can be selected and used as appropriate.

In the present invention, the above-described configuration according to the present invention can improve sensitivity fluctuation, density fluctuation, and gradation fluctuation in multiple exposure even when a large amount of printing is performed by a high-speed printer. In particular, a high-speed printer capable of outputting 1000 or more L-hour equivalent prints or more can exert the effects of the present invention, and more preferably a high-speed printer capable of printing 1500 L-hour prints or more. And Particularly preferred is a high-speed printer of 2000 sheets / L plate or more.

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

《Silver halide photographic photosensitive material: Preparation of sample 101》

(Preparation of silver halide emulsion)

Each silver halide emulsion was prepared by the following method.

(Preparation of red-sensitive silver halide emulsion)

In 1 liter of 2% gelatin aqueous solution kept at 40 ° C, the following (Solution A) and (Solution B) were added for 30 minutes while controlling pAg to 7.3 and pH to 3.0. Then, the following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling pAg at 8.0 and pH at 5.5. At this time, the pH was controlled by the method described in JP-A-59-4537, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(A liquid)

Sodium chloride 3.42 g Potassium bromide 0.03 g 200 ml with water

(Solution B)

Silver nitrate 10 g Add water 200 ml

(C solution)

Sodium chloride 102.7 g

_{K 2 I r C 16 X 10-} 8 mol / Monore A g _{K 4 F e (CN) 6} 2 X 1 0- 5 mole Z moles A g bromide force tumefaciens 1. 0 g Water to make 600 meters l

(D solution)

After adding 300 g of silver nitrate and 600 ml of water to complete the addition of each of the above solutions, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous magnesium sulfate manufactured by Kao Atlas. Emulsion EMP-1 was obtained as a monodisperse cubic emulsion having an average particle size of 0.40 m, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% by mixing with an aqueous gelatin solution.

Next, the average particle size was 0.38 in the same manner as in Emulsion EMP-1 except that the addition time of (A) and (B) and the addition time of (C) and (D) were changed. The emulsion EMP-1B was obtained as a monodisperse cubic emulsion having a m of 0.07, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.

The above emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimally chemical sensitizing the emulsion EMP-1B, the sensitized emulsion EMP-1 and the emulsion EMP_1B were mixed at a silver ratio of 1: 1. A red-sensitive silver halide emulsion (101R) was obtained.

Chio sulfate Na Application Benefits um 1 X 1◦- ⁴ mol / mol A g X chloroauric acid 1. 2 X 10- ⁴ Morunomoru A g X Stabilizer: S TAB- 1 3 X 10- ⁴ mole Z moles A g X stabilizers: S tAB- 2 3 X 10- ⁴ mole Z moles A g X stabilizer: S tAB- 3 3 X 10- ⁴ mole Z moles A g X Sensitizing dye: RS- 1 1 X 10- ⁴ mole Z moles A g X Sensitizing dye: RS- 2 1 X 10- ⁴ mole Z moles A g X

S TAB— 1: 1— (3-acetamidophenyl) -1-5-mercaptotetrazole

S TAB-2: 1-Phenyl-5-mercaptote tolazole

S TAB-3: 1- (4-ethoxyphenyl) -1-5-mercaptotetrazo

Also the red-sensitive emulsion, SS- 1 was added per mol of silver halide 2. 0 X 10- ^3.

(Preparation of green photosensitive silver halide emulsion)

In the preparation of the above emulsion EMP-1, the average particle size was 0.40 m in the same manner except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed. The emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Next, in the preparation of the emulsion EMP-1, the average particle size was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle size of 50 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.

The emulsion EMP-2 prepared above was optimally chemically sensitized at 55 ° C using the following compounds. Similarly, after optimally chemical sensitizing the emulsion EMP-2B, the sensitized emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1. To obtain a green photosensitive silver halide emulsion (101G).

Chio sulfate isocyanatomethyl Li um 1 X 10- ⁴ mol / mol A g X chloroauric acid 1. 2 X 10- ⁴ mole Z moles A g X Stabilizer: STAB- 1 2. 5 X 1 0 one ⁴ mol / mol A gx Stabilizer: STAB- 2 3. 1 X 1 0- 4 mol / mol A gx Stabilizer: STAB- 3 3. 1 X 1 O — ⁴ mol / mol Ag X sensitizing dye: GS-1 X 10_ ⁴ mol / mol Ag X (Preparation of blue-sensitive silver halide emulsion)

In the preparation of the emulsion EMP-1, the average particle size was 0.71 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a size of μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Also, in the preparation of the emulsion EMP-1, the average particle size was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-3B was obtained as a monodisperse cubic emulsion having a length of 64 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.

The above emulsion EMP-3 was subjected to optimal chemical sensation at 60 ° C using the following compounds. Similarly, after optimally chemical sensitizing Emulsion EMP-3B, 增 Emulsified EMP-3 and EMP-3B were mixed at a silver ratio of 1: 1. Then, (101 B) was obtained.

Chio sodium sulfate 1 X 1 0- ⁴ mol / mol A g X chloroauric acid 1. 2 X 1 0- ⁴ mol / mol A g X Stabilizer: STAB- 1 2 X 1 0- ⁴ mol / mol A g X stabilizer: STAB- 2 2. X 1 0- ⁴ mol / mol A g X stabilizer: STAB- 3 2. 1 X 1 0- 4 mol Z moles A g X sensitizing dye: BS _ 1 X 1 0 — ⁴ mol / mol Ag X 增 Dye: BS-21 1 X 10 — ⁴ mol / mol Ag X 26

BS-1

(CH ₂ ) ₃ S0 ₃

<< Production of silver halide photographic light-sensitive material >>

On both sides of paper pulp having a basis weight of 180 g / m ^2, laminated with high density polyethylene A reflective support was prepared. However, on the side to which the photosensitive layer was applied, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated.

After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further provided thereon, to prepare Sample 101 as a silver halide color photographic light-sensitive material. The coating solution was prepared as described below.

(Preparation of first layer coating solution)

Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST_1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stin prevention 0.34 g of agent (HQ-1), 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and 1.67 g of high-boiling organic solvent (DNP), and 60 ml of ethyl acetate The solution was then emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to obtain a yellow coupler dispersion. Prepared. The yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion (101B) prepared above to prepare a first layer coating solution.

(Preparation of coating solution for 2nd to 7th layers)

The coating liquids for the second layer to the second layer were prepared using the following additives in the same manner as in the preparation method of the first layer coating liquid.

(Configuration of sample 101)

7th layer: protective layer> g / m ² gelatin 1.00 DIDP 0.0 O 5 Silicon dioxide 0.0003 layer 6: UV absorbing layer>

Gelatin 0.40 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0.04 PVP ( Polyvinylpyrrolidone) 0.03. Anti-irradiation dye (AI-1) 0.011 (5th layer: red-sensitive layer)

Gelatin 1 30 Red light-sensitive silver halide emulsion (10 1 R) 0 21 Cyan coupler (C-1) 0 25 Cyan coupler (C-2) 0 08 Dye image stabilizer (ST-1) 0 10 Sting inhibitor (HQ -1) 0 004 D 0 P 0 34 4th layer: UV absorbing layer>

Gelatin 0.94 UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Sting inhibitor (HQ-3) 0.10 Anti-irradiation dye (AI-1) 0.02 Third layer: Green photosensitive layer>

Gelatin 1 30 Green photosensitive silver halide emulsion (101G) 0 1 Magenta coupler (M-1) 0 20 Dye image stabilizer (ST-3) 0 20 Dye image stabilizer (ST-4) 0 17 DIDP 0 13 DBP 0 13 Anti-irradiation dye (AI-2) 0 01 2nd layer: middle layer>

Gelatin 1 20 Stin inhibitor (HQ-2) 0 03 Stin inhibitor (HQ-3) 0 03 Stin inhibitor (HQ-4) 0 05 Stin inhibitor (HQ-5) 0 23 DIDP 006 Optical brightener (W- 1) 0 10 Irradiation dye (AI-3) 0 01 <First layer: blue-sensitive layer>

Gelatin 1.20 Blue-sensitive silver halide emulsion (101B) 0.26 Yellow coupler (Y—1) 0.70 Dye image stabilizer (ST_1) 0,10 Dye image stabilizer (ST-2) 0,10 Stain inhibitor (HQ-1) 0,01 Dye image stabilizer (ST-5) 0, 10 Image stabilizer A 0, 15 DNP 005 DBP 0.10 Support: Reflective support 1 Polyethylene laminated paper (contains a trace amount of colorant) The amount of each silver halide emulsion mentioned above is Converted and displayed. Further, (H-1) and (H-2) are added to each of the above coating solutions as a hardening agent, and surfactants (SU-2) and (SU-3) are used as coating aids. Was added to adjust the surface tension. Preservative F-1 was added as appropriate.

S U-1: Tri sodium i-propyl naphthalene sulfonate

S U-2: Sulfosuccinate di (2-ethylhexyl) 'sodium salt

S U—3: di-sulfosuccinate (2,2,3,3,4,4,5,5-taktolopentyl) and sodium salt

DBP: dibutyl phthalate

DN P: dinonyl phthalate

D 0 P: Dioctyl phthalate

DIDP: Di-i-decylphthalate

H-1: Tetrakis (vinylsulfonylmethyl) methane

H-2: 2,4-dichloro-6-hydroxy_s-triazine 'sodium

HQ—1: 2,5—G-t-octyl high droquinone HQ—2: 2,5-di-sec—dodecylhydroquinone

HQ-3: 2,5-di-sec-tetradecylhydroquinone

HQ—4: 2—sec—dodecinoleone 5—sec—tetradecinolenodidroquinone

HQ—5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone.

Image stabilizer A: P-t one-year-old octylphenol

Y— 1

M-1

c-1

C-2

S— 丄 S

17— 丄 S οτ

£ — 丄 S

Ζ— 丄 S

Ray S

886000 / C00Zdf / X3d 6 £ Z890 contract OAV UV— 2

UV— 3

1-1

AI-2

AI-3

W-1

F-1

,,, +

C to S CH ₃

(50%) (46%) (4%) Molar ratio The logarithmic value of the exposure amount (Eo. ₃ ) that gives the reflection density of 0.3 measured on the sample 101 prepared above by the method described later, and E _max AL 0 g E is 0.33 for the blue-sensitive yellow-color image forming layer (first layer), 0.32 for the green-sensitive magenta image forming layer (third layer), and red It was 0.34 in the photosensitive cyan image forming layer (fifth layer).

(Preparation of Sample 102)

In the preparation of Sample 101, the silver halide amount and the coupler addition amount of the first layer (blue-sensitive layer), the third layer (green-sensitive layer), and the fifth layer (red-sensitive layer) were appropriately increased. A sample 102 was prepared in the same manner except that AL og E was 0.39 for the first layer, 0.40 for the third layer, and 0.37 for the fifth layer.

(Preparation of Sample 103)

In the preparation of the above sample 1◦1, when the emulsions used in the first layer (blue-sensitive layer), the third layer (green-sensitive layer) and the fifth layer (red-sensitive layer) were chemically sensitized, Sodium sulfate Change the amount of beam to 0. 5 X 1 0- ⁴ mol Z moles A g X, is in the same manner except for adding further preparative Rifuwenirufu Osufi Nserenido a 0. 5 X 1 0- ⁴ mol / mol A g X Thus, Sample 103 was prepared.

[Preparation of Sample 10: ~ 109]

In the preparation of Sample 103, the amounts of silver halide and couplers in the first layer (blue-sensitive layer), the third layer (green-sensitive layer), and the fifth layer (red-sensitive layer) were appropriately changed. Samples 104 to 109 having ΔL 0 gE shown in the following table were prepared in the same manner except for the above.

[Preparation of Sample 110]

In the preparation of Sample 109 above, in the preparation of each photosensitive silver halide emulsion, a chemical sensitizer (sodium thiosulfate, trifrinylphosphine serenide, chloroauric acid) and a stabilizer (ST By changing the amount of AB_1 to STAB-3) and the chemical sensitization conditions (temperature and time) as appropriate, each photosensitive silver halide emulsion with different suitability for multiple exposure was prepared and used. A sample 110 was prepared in the same manner except for the above.

[Preparation of sample 1 1 1]

In the preparation of Sample 110, Sample 11 was prepared in the same manner except that the amounts of couplers of the first layer, the third layer, and the fifth layer were appropriately changed and the Dma X balance was changed. . * 1 ΔL 0 g E Remarks

Y M C

10 1 1/0 0.33 0.32 0.34 Comparative example 102 / O 0.39 0.40 0.37 Ratio father

103 0.5 / 0.5 0.5 0.30 0.33 0.3 1

104 0.5 / 0.5 0.5 0.64 0.65 0.63

105 0.5 0.5 0.5 0.5 0.5 0 32 0.552

106 0.5 0.5 0.5 0.51 0.52 0.52 The present invention 107 0.5 / 0.5 0.50 37 0.38 0.36 The present invention

108 0.5 / 0.5 0.5 0.57 .0.59 0.58

109 0.5 / 0.5 0.5 0.5 1 0.52 0.52

1 10 0.5 / 0.5 0.5 0.5 1 0.52 0.52

1 1 10.5 / 0.5.0.5 1 0.52 0.52 The present invention * 1: The chalcogen sensitizer of each of the first, third and fifth layers of the photosensitive silver halide emulsions Constituent ratio (molar ratio): sodium thiosulfate / triphenylphosphine resin

《Evaluation of silver halide photographic light-sensitive material》

(Exposure)

Scanning exposure and processing as described below were performed on each sample manufactured as described above. For scanning exposure, a semiconductor laser (oscillation wavelength 650 nm), He-Ne gas laser (oscillation wavelength 544 nm), and an Ar gas laser (oscillation wavelength 45 8 nm), the amount of light for each laser beam is modulated by AOM based on image data, reflected on polygons, and main scanning is performed on the photosensitive material. The photosensitive material was conveyed vertically (sub-scan). At this time, it was confirmed using a beam monitor that the beam diameter was 100 m for each of B, G, and R. Reproduction of image data (R, G, B) = (0, 0, 0) created on the print with the target maximum density value (Ph0t0sh0p5.0 (manufactured by Adobe)) Target value), (R, G, B) = (2.30, 2.17, 1.

97), from the lowest density to the highest density, it is divided into 21 steps, and the output of the gray patch is performed. From the density measurement result of the gray patch obtained by processing by the following development process, The work of rewriting the control conversion table (C-LUT) that associates data with the exposure control value (calibration) was repeated three times. In each case after the three calibration operations, the target density set in advance in the conversion table (D-LUT) that associates the image data with the target density, and the actual printed patch It was confirmed that the difference from the concentration was within 5% of the target concentration on average. At the end of the calibration process, the exposure required to obtain the highest density was read from the control conversion table, and the maximum exposure (EmaX) for each image forming layer was determined.

With the target maximum density set and calibration completed in this way, each sample is subjected to scanning exposure based on the image data created on PhotoShop 5.0, and the Processing was performed. The image data used is created at a resolution of 300 dpi, and has a 1-pixel wide black line ((R, G, B) = (0, 0, 0)) pattern and three types of black data (( R, G, B) = (0, 0, 0), 2 drawn as (13, 13, 13) ヽ (26, 26, 26)) Point and 4-point text images, black background ((R, G, B) = (0, 0, 0)) and white ((R, G, B) = (255, 255, 255)) It consisted of a combination of a single patch group, a patch group of yellow, magenta, and cyan, and a sharpness chart image created by combining white character text images and RGB image data with little change. In the present invention, dpi refers to the number of dots per 2.54 cm.

In each print image obtained in this way, the density of the gray patch group was measured with an Xite 938 reflection spectrophotometer / densitometer (manufactured by X-Rite), and the status A reflection density was (R , G, B) = (0.30, 0.30, 0.30) From the image data of the patch and the control conversion table, in each image forming layer, an exposure amount (Eo ₃ ) was asked. From these, L og E (D max) L og E (Do. 3) was obtained, and the difference was defined as AL og E.

In addition, for each of the photosensitive material samples prepared in this manner, a helium-power laser beam (about 422 nm) was used as the blue light source, a purple neon laser (about 544 nm) as the green light source, and a red light source (about 544 nm). An optical system using a gallium aluminum arsenic semiconductor laser (approximately 780 nm) as the light source. A beam diameter of approximately 80 m, a polygon mirror is used, and a scanning speed of 16 Om / s, 1 pixel The following three types of exposure were performed under the conditions of an exposure time of 5 × 10 ¹⁷ seconds.

1: A sample that has been subjected to gray-scale exposure once and a sample that has been subjected twice by controlling the exposure amount using an external modulator.

2: Sample subjected to uniform scanning exposure to obtain a patch with a density of 1.0 [Development processing]

Each of the exposed samples was subjected to the following development processing. <Development process>

Process treatment temperature Time replenishment rate color developing 38. 0 ± 0. 3 ° C 45 seconds 80 m 1 / m ² blix 3 5. 0 ± 0. 5 ° C 45 sec 1 20 m 1 / m ² depreciation in the constant I inhibit 3 0-34 6 0 seconds 1 50 m 1 / m ² drying 6 0 to 80 ° C 3 0 seconds

The composition of each developing solution used in the developing step is shown below.

Color developing solution>

Tank liquid Replenisher Pure water 8000 ml 800 ml ml Triethylene diamine 2 g 3 g Nethylen konori 10 g 10 g Lithium bromide 0.0 1 g

3.5 g of potassium chloride

Potassium sulphite 0.25 g 0.5 g

ェ —Ethyl Ν— (β-methanesulfonamidoethyl) ― 3-methyl-4-aminoaminolinyl sulfate 6.0 g 1 0.0 g

Ν, Ν-Jetylhydroxylamine 6.8 g 6.0 g Triethanolamine 1.00.0 g10.0 g (4, 4'-Diaminostilbene disulfonic acid derivative)

2.0 g 2.5 g Carbonated rim 30 g 30 g The total volume was adjusted to 1 liter by adding water, and the pH of the tank solution was adjusted to 10.10 and the pH of the replenisher was adjusted to 10.60.

Bleach-fixer: tank solution and replenisher>

Diethylene triammonium pentaacetate diammonium dihydrate 65 g Getilent rimamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml water was added to make up the whole volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution: tank solution and replenisher>

o-Phenylphenol l. O g 5-Chloro-2-methyl-1-4-isothiazolin-3-one 0.02 g

2-Methyl-1-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopal S FP) 2.0 g

1-Hydroxyshethylidene_1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate / 7 hydrate 0.2 g PVP l. O g Ammonia water (ammonium hydroxide 2.5 g Trisodium triacetate trisodium salt 1.5 g Water was added to make up to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia. I adjusted it.

(Evaluation of suitability for multiple exposure)

For each sample subjected to the above exposure and color development processing, the obtained gradation image was measured with a reflection densitometer (X-Rite 938 manufactured by X-Rite), and the horizontal axis was the exposure amount (L ₀ g E), vertical axis: After creating a characteristic curve consisting of the color density (D), the gradient ry of the density change with respect to the exposure amount between each density 0.5 and 1.5 of yellow, magenta, and cyan images. For rm, rc, tilt at l exposures? The absolute value of the rate of change of the slope r2 in the _two exposures to ^ was determined as the gradation variation rates Δry, Arm, and Arc according to the following equation, and this was used as a measure of the suitability for multiple exposure.

Gradation change rate (%) = {| 2— r i Zr i} x i o o

(Measurement of each maximum concentration D _max )

For the color development processed samples, using a reflection densitometer (X- R ite Co. X- R ite 938), Y, M, the maximum concentration of C (D _maxBヽ_D maxG, D _maxR) was measured , 0 „^ _; : 0 ₁ „ ^ ₍₅ and 13 ₁ ^ _! ^ 70 ₁ ^^ were determined.

(Evaluation of sharpness)

The sharpness chart image of each sample prepared above was visually observed by 10 people. If there were ◎, 7 or 8 〇, 5 or 6 △, and 4 or less X.

(Evaluation of suitability for high-speed digital printing)

Using each sample, with a high-speed laser printer (Noritsu QS S 3101 digital printer manufactured by Noritz), it is possible to obtain a patch with a density of 1.0 under the condition of 2350 sheets per hour of L plate. Uniform scanning Pre-exposed image for 1 hour After the printing, the following evaluation was performed for the variation in the image density portion of the final print.

Evaluation of variation in image density area>

Using a reflection densitometer on the patch of the final print with a density of 1.0, measure the reflection density of each color at 5100 points, and find the difference (ι.ο) between the maximum density and the minimum density. The average value of the differences was used as a measure of the variation in the image density portion.

The results obtained above are shown in the table below.

Multiple exposure suitability D _max / Lance 氺丄 1 PR F0 =

Sharpness

Λ

y H γ m m r c B / G R / G 丄 U 丄 b 1 1 0 .61 0 .62 U · u 1, /

y X Comparative example 丄 U ^ 丄 1

b 13 12 0 .63 0 .61 U. U 1 o X

早 U d 丄 (15 '10 .63 0 .62 u · U 1 O X ΐΏ \

4 丄 b 19 18 0 .62 0 • 62 r

U 11 U o Λ レレレレ n n 1 n U O 丄 ί 13 1 0. 63 0 • 62 U.

7 Comparative example 丄 U 1

b ワ Wah ί A 1 A

b 丄 r 0 .64 u. Ό O U. (J11 υ 9 Description 107 16 1 1 0 .63 0 .62 0. 013 〇 The present invention

108 18 16 15 0 .64 0 .62 0 .012 〇 The present invention

109 9 98 0 .63 0 .64 0 .009 ◎ The present invention

110 9 98 0 .89 0 .93 0 .006 The present invention

111 9 9 8 1.36 1.37 0. 0 9 ◎ The present invention * 1: The image density area after printing for 1 hour continuously with a high-speed digital printer.

As is evident from the above results, samples 106 to 111 using the selenium compound and having a structure defined by the present invention in which Δ.Log E is in the range of 0.35 to 0.6 in all three layers are: Compared to the comparative example, even after continuous printing with a high-speed digital printer, a stable image was obtained with less variation in the image density portion. In addition, an image having excellent image clarity was obtained. Also, it can be seen that the effects of the present invention are greater in the samples 109 to 111 in which the gradation variation in the multiple exposure is less than 10%. In addition, it can be seen that the sample 110 in which each _Dmax concentration ratio is in the range of 0.7 to 1.3 has a greater effect of the present invention.

As described above, the sample having the configuration specified by the present invention has less variation in the image density portion and excellent sharpness even after continuous printing with a high-speed digital printer compared to the comparative example. It was confirmed that a stable image could be obtained. Industrial potential

As described above, according to the configuration of the present invention, even after continuous printing with a high-speed digital printer, an image forming apparatus that can provide a stable image with less variation in the image density portion and excellent sharpness can be obtained. A method can be provided.

Claims

The scope of the claims

1. A silver halide having at least one blue-sensitive yellow monochromatic image forming layer containing a photosensitive silver halide, at least one green-sensitive magenta image-forming layer and at least one red-sensitive cyan image-forming layer on a support In an image forming method that performs a color developing process after subjecting a color photographic material to scanning exposure with a light beam so that the exposure time per pixel is 10 to ³ seconds or less, the output of a calibration patch adjusts the maximum exposure amount at the time by Ri image formed _(E raax), and said silver halide color one photographic light-sensitive material, the logarithm of the exposure amount (E .. ₃₎ providing a reflection density 0.3 , difference AL o _g E between the logarithmic value of the E _m _ax is該青photosensitive yellow color image forming layer, green light sensitive magenta image forming layer and a red-sensitive cyan color image forming layer, each 0.3 5 or more,

0.6 or less, and at least one of the color image forming layers contains silver halide chemically sensitized with a selenium compound.

2. The horizontal axis is obtained by performing exposure and color development processing in ^10-6 seconds or less exposure time: exposure (L og E), vertical axis: on the characteristic curve consisting of color density, a density 0.5 2. The image forming method according to claim 1, wherein the variation of the average gradient of a straight line passing through the point to be given and the point to give a density of 1.5 is within 10% in multiple exposure.

3. The above-mentioned silver halide color photographic light-sensitive material is subjected to exposure and color development processing with an exposure time of 90 seconds and 10 to ¹⁶ seconds to obtain a yellow one-color image (B), a magenta color image (G), and cyan. the concentration ratio of each maximum density D _max on the characteristic curve of the color image _{_{(R) (D maxB ZD raaxG}} , D maxR / D maxG) are each 0. 7; the range of L. 3 The image forming method _{c according} to claim 1 or 2, wherein