JP2006227164A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method which improves image distortion in a peripheral exposure region and ensures excellent blurring resistance and color running resistance of characters and an image. <P>SOLUTION: In the image forming method, a reflection viewing type silver halide color photosensitive material is exposed using a digital image exposure device, wherein a pixel ratio (major side/minor side) of pixels to a region 10 cm away from the exposure center in the digital image exposure device is 1.00-1.03. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an image forming method in which a reflection viewing type silver halide color photosensitive material is exposed using a digital image exposure apparatus.

  In recent years, opportunities for handling images as digital data are rapidly increasing in accordance with the improvement of computing power of computers and the advancement of network technology. Image information converted into digital data using a scanner or the like can be edited and processed on a computer, and data such as characters and illustrations can be added relatively easily. Hard copy materials for producing hard copies based on such digitized image information include, for example, sublimation type thermal transfer prints, melt type thermal transfer prints, ink jet prints, electrostatic transfer type prints, thermoautochrome prints, halogens. Examples include silver halide color photographic light-sensitive materials. Among them, silver halide color photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) have high sensitivity, excellent gradation, and image storability. Since it has excellent properties compared to other printing materials such as superiority, it is actively used today as a recording material for producing high-quality hard copies.

  In order to reproduce digitized image data as a silver halide color photograph, it is necessary to perform exposure while changing the exposure amount according to the image data. The digitized image data includes, for example, character images, particularly thin and small black character images, in addition to images based on photography data such as people, landscapes, and still life (hereinafter also referred to as “scene images”). The ratio of handling white text images is increasing. In particular, in a fine character image composed of fine lines, a phenomenon that the edges of the fine lines appear to be different from the original character color (hereinafter also referred to as “color blur”) may easily occur. This phenomenon is particularly remarkable in digital exposure in which a light beam with high illuminance is exposed in a short time, and various techniques relating to a silver halide color photographic light-sensitive material suitable for digital exposure for improving this phenomenon have been disclosed. (For example, refer to Patent Documents 1 to 5.)

  However, as the digital exposure suitability of the silver halide color photographic light-sensitive material has improved, image quality deterioration due to the adjustment shift of the exposure unit of the exposure apparatus cannot be ignored. In particular, it has been found that when the maximum color density formed on the silver halide color photographic light-sensitive material at the time of exposure is high, the influence appears remarkably. In recent years, scanning exposure apparatuses using a He—Ne gas laser, a semiconductor laser, and an Ar gas laser have been frequently used in professional laboratories. In this method, scanning exposure is performed from the central part to the peripheral part by changing the angle of the polygon mirror located far from the center part. However, the shape of the pixel by this method differs between the central part and the peripheral part, and the beam spot is in the peripheral part. The more you go, the harder it gets to be perpendicular to the page. In printing, this ellipse shape is negligibly small in service size, but in professional labs it is printed in large size such as 12 inch size (here 1 inch represents 2.54 cm). However, in such a large size print, the elliptical pixel shape has a large influence on the final image quality characteristics, which is a problem.

  On the other hand, for example, there has been proposed an apparatus that scans a deflected light beam in a dot shape by a reflection imaging optical system (see, for example, Patent Document 6), but this method is applied. However, it is impossible to correct the peripheral pixels from becoming elliptical during exposure. That is, basically, in the exposure method using a polygon mirror, it is impossible to avoid the peripheral pixels from becoming ellipses in principle.

  On the other hand, as a method for forming an image on a silver halide color photographic light-sensitive material as a recording material, for example, a print head having an optical shutter composed of a PLZT (Plomb Lanthanum Zirconate Titanate) element is turned on pixel by pixel. There is known a method of forming an image by controlling / OFF.

  Various proposals have been made in order to improve the image quality of an image recorded by the print head. For example, when a recording operation by an optical shutter is on standby, a residual light is emitted by flashing a light source and irradiating a PLZT element. There is known a method of improving the image quality by eliminating the photo-induced birefringence and avoiding the decrease in photoelectrically induced birefringence (for example, see Patent Document 7).

However, the method described in Patent Document 7 cannot suppress density unevenness caused by fluctuations in image density in the main scanning direction. This unevenness in image density is caused when the number of PLZT elements in the driving state changes rapidly in a short time, and load fluctuation occurs at the start of driving of each PLZT element. As a result, the density of the image recorded by the PLZT element temporarily changes. By fluctuating. Specifically, for example, when an image is recorded by conveying a recording material in a direction (sub-scanning direction) orthogonal to the arrangement direction (main scanning direction) of the PLZT elements, by driving all the PLZT elements The image density recorded continuously in the main scanning direction and the density of the image recorded by driving 10% of the entire PLZT element at the same density as the image in a region adjacent to the image are the PLZT element. Therefore, it is recognized as density unevenness.
JP 2000-19696 A JP 2000-227638 A JP 2000-35295 A Japanese Patent Laid-Open No. 2001-324783 JP 2004-170949 A JP 2003-107383 A JP 2000-347150 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an image forming method that improves pixel distortion in the peripheral exposure amount region and has excellent blur resistance and color blur resistance of a character image. .

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

(Claim 1)
An image forming method in which a reflection viewing type silver halide color light-sensitive material is exposed using a digital image exposure apparatus, the pixel ratio (long) of a pixel to an area 10 cm away from an exposure center in the digital image exposure apparatus Side / short side) is 1.00 or more and 1.03 or less.

(Claim 2)
The digital image exposure apparatus has an arrayed recording head, and the reflection viewing type silver halide color photosensitive material is moved while the recording head and the reflection viewing type silver halide color photosensitive material are moved relative to each other. 2. The image forming method according to claim 1, wherein an image is recorded.

(Claim 3)
The recording head includes a plurality of recording element chips each including a plurality of recording elements, and includes a driving unit that drives the plurality of arranged recording elements, and the driving start timing of the driving unit is set at predetermined intervals. 3. The image forming method according to claim 2, further comprising drive control means for performing shifting control.

(Claim 4)
The image forming method according to claim 3, wherein the driving unit is provided for each of the one or more recording element chips, and the predetermined interval is 1.0 μs or more.

(Claim 5)
5. The recording head according to claim 2, wherein the recording head has a light source having light source colors of R (red), G (green), and B (blue), and the light source is an LED light source. The image forming method according to item.

(Claim 6)
The reflection reflectance-type silver halide color light-sensitive material has a maximum reflection density after development of a blue image density of 2.2 or higher, a green image density of 2.4 or higher, and a red image density of 2.3 or higher. The image forming method according to claim 1, wherein:

(Claim 7)
The reflection reflection type silver halide color light-sensitive material has a maximum reflection density after development of a blue image density of 2.35 ± 0.05, a green image density of 2.55 ± 0.05, and a red image density of 2. The image forming method according to claim 1, wherein the image forming method is .55 ± 0.05.

  ADVANTAGE OF THE INVENTION According to this invention, the pixel distortion in a peripheral exposure amount area | region can be improved, and the image formation method excellent in the blur tolerance of a character image and the color bleeding resistance can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor is an image forming method for exposing a reflection viewing type silver halide color light-sensitive material using a digital image exposure apparatus, in the digital image exposure apparatus. By using an image forming method characterized in that the pixel ratio (long side / short side) of pixels from the exposure center to a region 10 cm away is 1.00 or more and 1.03 or less. As a result, the present inventors have found that an image forming method capable of improving pixel distortion in a region and realizing an excellent blur resistance and color blur resistance of a character image can be realized.

  First, a digital exposure apparatus according to the present invention will be described.

  As mentioned above, color printing using a 12-inch large reflective reflection-type silver halide color light-sensitive material in professional specifications, especially in the exposure method using a polygon mirror, the exposure center is exposed. In the peripheral portion, the pixels are distorted and the pixels have a large pixel ratio, which causes blurring and color blurring of the character image. The pixel ratio here refers to the ratio of the length in the major axis direction to the length in the minor axis direction at the exposure spot of one pixel.

  In the digital image exposure apparatus according to the present invention, the pixel ratio (long side / short side) of pixels up to a region 10 cm away from the exposure center is 1.00 or more and 1.03 or less. .

  As a method for setting the pixel ratio (long side / short side) of pixels from the exposure center defined by the present invention to a region 10 cm away from 1.00 to 1.03, a plurality of recording elements are arranged in an array. A digital image exposure apparatus that performs recording on the silver halide color photographic light-sensitive material while relatively moving the recording head and the silver halide color photographic light-sensitive material. The head is configured by arranging a plurality of recording element chips composed of a plurality of recording elements, and a plurality of drive units for driving the arranged plurality of recording elements are provided, and the drive start timing of the drive unit is set. It is preferable to use a digital image exposure apparatus provided with a drive control means for performing control to shift a predetermined interval. In the present invention, a PLZT (Plomb Lanthanum Zirconate Titanate) element is used as the plurality of arrayed recording elements, and the pixel ratio (long side / short side) of pixels up to a region 10 cm away from the exposure center is expressed as follows. It is preferable at the point which can be set to 1.00 or more and 1.03 or less.

  In addition, by applying the digital image exposure apparatus according to the present invention having the above-described configuration, the recording head is driven at a different driving start timing for each driving unit. As a result, even when the image density in the arrangement direction of the recording elements changes abruptly, all of the recording elements that perform recording are not simultaneously driven (voltage is applied), and the drive start timing is shifted. Thus, it is possible to prevent the number of recording elements to which a voltage is applied from changing rapidly. Therefore, the load fluctuation of the applied voltage to the recording element can be suppressed low, and a high-quality image with little density unevenness can be formed.

  Furthermore, in the digital image exposure apparatus according to the present invention, it is preferable that one or a plurality of recording element chips has the driving unit, and the predetermined interval is 1.0 μs or more.

  By shifting the driving start timing by 1.0 μs or more, even if a load fluctuation of the voltage applied to the recording element occurs, the unevenness of the image density due to the load fluctuation is lower than the visual recognition level. Unevenness is not noticeable, and a higher quality image can be formed.

  In the digital image exposure apparatus according to the present invention, the recording head has a light source composed of R (red), G (green), and B (blue) light source colors, and the light source is an LED light source. This is preferable in that the distortion (pixel ratio) of the pixels in the peripheral portion of the exposure, which is the object effect of the present invention, can be effectively suppressed.

  Further, the digital image exposure apparatus according to the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the example illustrated here. In addition, there are cases where the expression is limited, but this is not a limitation.

  FIG. 1 is a schematic configuration diagram of a 400 dpi photographic digital printer (hereinafter also simply referred to as a printer) 1 to which the present invention is applied. In the present invention, dpi is used as a unit of the number of pixels, and this represents the number of dots per 2.54 cm.

  The printer 1 includes a transport mechanism 2 for transporting a silver halide color photographic light-sensitive material 3 as a recording material in the X direction as a transport direction (sub-scanning direction), and a direction orthogonal to the X direction (main scanning direction). The exposure mechanism 4 as a recording head, the light source color switching unit 5, the driver IC 6, and the transport mechanism 2 are driven to form an image on the silver halide color photographic light-sensitive material 3 in a line along a certain Y direction. The light source color switching unit 5, the driver IC 6, and the conveyance drive unit 7 are based on the conveyance drive unit 7 to be performed and the input image data (hereinafter referred to as “image data”) of RGB exposure colors (light source colors). The exposure control unit 8 performs control, and a support member 9 that supports the silver halide color photographic light-sensitive material 3 from below at an exposure portion exposed in a line by the exposure mechanism 4.

  The conveyance mechanism 2 includes driving rollers 21 and 21 that rotate around an axis perpendicular to the X direction by power of a motor or the like, and press-contact rollers 22 that are in parallel with the driving roller 21 and press-contact with the driving rollers 21. 22, one drive roller 21 and the pressure roller 22 are arranged on the upstream side in the X direction, and the other drive roller 21 and the pressure roller 22 are provided on the downstream side in the X direction. The silver halide color photographic light-sensitive material 3 unloaded from the supply position (not shown) is sandwiched between the driving roller 21 and the pressure roller 22 and is conveyed in the X direction by the rotation of the driving rollers 21 and 21. It has become.

  The silver halide color photographic light-sensitive material 3 is a reflection-viewing type silver halide color light-sensitive material, and a color developing layer for forming each color forms a layer structure. A layer that forms a cyan image after color development processing is exposed from the side closer to the surface, and a layer that forms a magenta color image after exposure to green light (G). And a layer for forming a yellow color image after color development processing. The silver halide color photographic light-sensitive material 3 is wound in a roll shape at a supply position (not shown).

  The exposure mechanism 4 is a light source having light source colors of R (red), G (green), and B (blue). In the present invention, it is particularly preferable to use the LED light source 41. The LED light source 41, an exposure head 42 disposed opposite to the silver halide color photographic light-sensitive material 3 between the two drive rollers 21, and the exposure head 42 and the silver halide color photographic light-sensitive material 3 are provided. Selfoc lens array 43, optical fiber array 44 for guiding light from LED light source 41 to exposure head 42, one end of optical fiber array 44, integrator 45 interposed between LED light sources 41, and the like. It is prepared for.

  The silver halide color photographic light-sensitive material 3 is transported by the transport mechanism 2 and moves relative to the exposure mechanism 4 so that an image corresponding to the image data is recorded.

  The exposure head 42 is, for example, a PLZT shutter array head in which PLZT (Plumb Lanthanum Zirconate Titanate) elements as a plurality of recording elements are arranged in an array along the Y direction as pixels of light emission points.

  Specifically, the exposure head 42 forms an array by arranging a plurality of PLZT chips 421 composed of a plurality of PLZT elements 425 on a ceramic or glass substrate (not shown) having a slit-shaped opening, and A plurality of driver ICs 6 as drive units are arranged on both sides of a plurality of PLZT chips 421.

  As shown in FIG. 2, the PLZT chip 421 has a three-dimensional shape, and is provided with a PLZT element 425, individual electrodes 422, a common electrode 423, and the like.

  Specifically, a large number of PLZT elements 425 corresponding to one pixel are arranged in two columns, and each PLZT element 425 is formed in a staggered pattern by one pixel, so that two columns (Odd column, even column) are main. An image of one line is formed in the scanning direction Y.

  The common electrode 423 is provided in common for the odd and even rows, and the individual electrode 422 is provided separately for the odd and even rows, and is provided individually for each PLZT element 425. Further, both electrodes 422 and 423 are provided on both sides of the PLZT element 425 in parallel to the optical path, and have a structure capable of realizing a large light transmission amount even with a low applied voltage.

  The driver IC 6 is a drive circuit for driving the PLZT element 425 by changing the applied voltage applied to the exposure head (the individual electrode 422 and the common electrode 423), that is, for applying a voltage to the PLZT element 425. The PLZT element 425 in the odd row and the PLZT element 425 in the even row are individually driven.

  As is well known, PLZT is a translucent ceramic having an electro-optic effect with a large Kerr constant, and the light linearly changed by a polarizer (not shown) is applied to the PLZT element 425 by the driver IC 6. Is turned on, the polarization plane is rotated, and the light is emitted from an analyzer (not shown). When the voltage is off, the plane of polarization of the transmitted light does not rotate, and such transmitted light is cut by an analyzer (not shown).

  That is, the transmitted light is turned on / off by turning on / off the voltage applied to each PLZT element 425, and the light emitted from the analyzer (not shown) passes through the Selfoc lens array 43 and is silver halide color photographic light sensitive. An image is formed on the material 3. The PLZT element 425 is on / off controlled line by line (main scanning) based on the image data, and the silver halide is moved by this main scanning and movement of the silver halide color photographic light-sensitive material 3 in the X direction (sub scanning). A two-dimensional image is formed on the color photographic light-sensitive material 3.

  FIG. 3 shows a schematic diagram of the exposure head 42 in the present embodiment. In this embodiment, the exposure head 42 includes 12 PLZT chips 421a, 421b,..., 421l, 8 driver ICs 6a, 6b,. As shown in FIG. 3, a driver IC 6 is provided for each of the plurality of PLZT chips 421.

  On / off control of the PLZT chip 421 is performed for each driver IC 6. Therefore, when the driver IC 6a applies the applied voltage, the PLZT element 425 on the Odd column side of the PLZT chips 421a, 421b, 421c is driven. At the same time, when the driver IC 6e applies the applied voltage, the PLZT elements 425 on the even column side of the PLZT chips 421a, 421b, and 421c are also driven.

  By performing exposure while the PLZT element 425 transmits light, the exposure time is controlled according to the image data, and gradation is expressed. For example, when expressing a lower density, the exposure time is shorter, and when expressing a higher density, the exposure time is longer.

  The SELFOC lens array 43 is formed by integrating a plurality of optically equivalent SELFOC lenses in parallel with each other, and forms an image of light transmitted through the exposure head 42 on the silver halide color photographic light-sensitive material 3. . In other words, the object plane formed by the Selfoc lens array 43 matches the exposure head 42, and the image plane formed by the Selfoc lens array 43 matches the silver halide color photographic light-sensitive material 3. The exposure locations are in the form of a line along the scanning direction Y on the image plane formed by the SELFOC lens array 43, and the length of the exposure locations along the scanning direction Y is arranged at the exit points of the exposure head 42. It is substantially the same as the length.

  One end of the plurality of optical fibers is bundled at one end of the optical fiber array 44, and the end of the optical fiber array 44 is directed to the LED light source 41. At the other end of the optical fiber array 44, each end of the optical fiber is connected to a PLZT element 425, which is an optical shutter element.

  The integrator 45 is provided to efficiently guide the light from the LED light source 41 to the optical fiber array 44, disperse the luminance unevenness of the light source, and obtain a uniform illuminance distribution. Not composed of input lens, fly-eye lens, output lens, filter, aperture, etc.

  The light source color switching unit 5 switches the RGB light source colors (exposure colors) constituting the LED light source 41 by, for example, an ON / OFF instruction from the exposure control unit 8, and sequentially switches the color of the light to be exposed.

  The conveyance drive unit 7 drives the drive roller 21 to control the conveyance of the silver halide color photographic light-sensitive material 3.

  The exposure control unit 8 synchronously controls the light source color switching unit 5, the driver IC 6, and the transport drive unit 7, and includes a CPU (Central Processing Unit) 81, a RAM (Random Access Memory) 82, and a ROM (Read). Only memory 83).

  The CPU 81 performs various calculations, instructions to each functional unit, data transfer, and the like based on various programs stored in the ROM 83 in accordance with a predetermined timing.

  The RAM 82 is used for storing data processed by the CPU 81 under the control of the CPU 81 and outputting the stored data to the CPU 81.

  The ROM 83 mainly stores programs, data, and the like for performing various operations performed by the transport mechanism 2 and the exposure mechanism 4, and specifically, for example, as shown in FIG. A program 831, a drive control program 832, a photographic paper transport control program 833, and the like are stored.

  The light source color switching program 831 is a program for switching the light source colors of RGB multiple times of the number of light source colors (3), that is, six times while the recording head 42 moves by one pixel in the sub-scanning direction. Therefore, the CPU 81 controls the light source color switching unit 5 by executing the light source color switching program 831 and functions as a light source color switching unit.

  Specifically, for example, one line is recorded by switching the light source colors R, G, and B six times, that is, by switching the light source colors RGB twice.

  Here, in the 400 dpi printer 1, for example, if the output value of the output data per pixel (depth of the output signal value) is 11 bits (2048 gradations), recording with the light source color RGB is 10 bits (1024 gradations). ) Can be executed in the time required to reproduce the output value, and the control part sequence can be simplified.

  The drive control program 832 is a program for driving the exposure head. The CPU 81 controls the driver IC 6 by executing the drive control program 832 and functions as a drive control unit.

  Specifically, the CPU 81 as drive control means performs control to shift the drive start timing of each driver IC 6 by a predetermined interval.

  FIG. 4 is a diagram for explaining the driving of the exposure head 42 when the driver IC 6 is provided for each of the eight PLZT chips 421 and the drive start timing is divided into eight. Here, “shifting the predetermined interval” specifically means that each driver IC 6, that is, the timing of starting driving the PLZT chip 421 by 1.0 (μs), as indicated by R 1 to R 8 in FIG. Means shifting. Similarly, in the light source color G and the light source color B, as indicated by G1 to G8 and B1 to B8 in FIG. 4, the driving of each PLZT chip is started at different timings.

  Further, the CPU 81 performs control to switch the applied voltage applied to the driver IC 6 that drives each PLZT chip 421 in accordance with RGB light source colors, and functions as a drive control unit.

  FIG. 5 shows the transmittance distribution of the PLZT shutter for each light source color with respect to the applied voltage. (X), (y), and (z) respectively indicate transmittance distributions of 450 nm wavelength light, 530 nm wavelength light, and 700 nm wavelength light. That is, the transmittance distribution depends on the emission wavelength of each light source color, and the voltage indicating the maximum transmittance is different. Therefore, different applied voltages are applied according to the respective light source colors. At this time, if the applied voltages corresponding to the RGB light source colors are V (R), V (G), and V (B), as shown in FIG. 5, V (R)> V (G)> V (B ) Is preferable.

  Also, as shown in FIG. 4, assuming that the voltage application time for each RGB light source color is t (R), t (G), and t (B), t (R), t (G), and t (B). Is preferably 500 (μs) or less. This is because if it exceeds 500 (μs), it cannot be used for high-speed printing.

  More specifically, in the silver halide color photographic light-sensitive material 3, the layer that develops yellow when B is exposed has the highest sensitivity, and the layer that develops magenta when G is exposed next has the sensitivity. It is preferable to set the exposure time longer in the order of R, G, and B, because the layer that is high and develops cyan when exposed to R has the lowest sensitivity.

  In general, as a capability required for a photographic exposure device, a spec of L size 700 sheets / hour or more is required. Assuming an L-size feed length of 89 mm and a paper interval of 20 mm, a writing time of one line of 400 dpi is about 3.0 ms. In order to make the sub-scanning direction 800 dpi, 500 μs or less is essential.

  Further, the CPU 81 performs control to start driving each PLZT chip 421 after 10 (μs) has elapsed since the switching of the applied voltage, and functions as a drive control unit.

  The CPU 81 functions as a drive control unit by performing control to apply a voltage higher than the applied voltage for a predetermined time from the start of applying the voltage to the exposure head 42.

  Here, the “predetermined time” means a time during which an appropriate applied voltage can be applied without being affected by the impedance of the system at the start of driving of each PLZT chip 421, and is, for example, 50 (μs). .

  Further, the “voltage higher than the applied voltage” means a voltage at which an appropriate applied voltage can be applied to each RGB light source color at the start of driving of each PLZT chip 421, for example, 5 ( V) High voltage.

  The photographic paper conveyance control program 833 is a program for conveying the silver halide color photographic light-sensitive material 3, and the CPU 81 controls the conveyance control unit 7 by executing the photographic paper conveyance control program 833. .

  An example of driving of the exposure head 42 when the printer 1 described above records an image for one line according to the image data will be described with reference to flowcharts shown in FIGS.

  First, the CPU 81 determines whether or not there is input data in the exposure control unit 8 (step S1). When the CPU 81 determines that no image data is input (step S1; No), the printer 1 enters a standby state. When the CPU 81 determines that image data has been input to the exposure controller 8 (step S1; Yes), the CPU 81 selects a light source color based on the input image data and performs switching (step S2). Data relating to the switched light source color is stored in the RAM 82. In the present embodiment, the light source color is first switched to R.

  Next, the CPU 81 switches the voltage applied to each PLZT chip 421 to the applied voltage corresponding to the light source color based on the data relating to the light source color stored in the RAM 82 (step S3; drive control step). That is, as shown in FIG. 4, the voltage is switched to the voltage V (R), which is an applied voltage corresponding to R.

  Next, the CPU 81 starts applying a voltage to the exposure head 42. At this time, a voltage higher than the applied voltage is applied until 50 (μs) has elapsed from the start of voltage application (step S4; drive control step). That is, as shown in FIG. 4, the voltage V (Rh) is applied as a voltage 5 (V) higher than the applied voltage V (R).

  In step S5, the CPU 81 determines whether 50 (μs) has elapsed after starting to apply the voltage V (Rh) as a voltage higher than the applied voltage (step S5). When the CPU 81 determines that a predetermined time has elapsed (step S5; Yes), the application voltage is applied as the application voltage (V (R)) corresponding to the light source color (step S6). If it is determined that the predetermined time has not elapsed (step S5; No), the CPU 81 continues to apply the voltage V (Rh).

  Next, the CPU 81 determines whether or not a predetermined time has elapsed since the applied voltage was switched (step S7). That is, as shown in FIG. 4, it is determined whether t (R) as a predetermined time corresponding to the light source color R has elapsed.

  When the CPU 81 determines that the predetermined time t (R) has elapsed (step S7; Yes), the CPU 81 determines whether or not the light source color has been switched six times in total (step S8; light source color switching step). . On the other hand, when the CPU 81 determines that the predetermined time t (R) has not elapsed (step S7; No), the application of the applied voltage V (R) is continued.

  In step S8, if the CPU 81 determines that the light source color has not been switched a total of six times (step S8; No), the process proceeds to step S2, and the CPU 81 executes selection and switching of the light source color again, and step S8. The process up to is executed. That is, as shown in FIG. 6, the processing from step S2 to step S8 is executed for the light source color G and the light source color B.

  If the CPU 81 determines in step S8 that the light source color has been switched six times (step S8; Yes), the driving of the exposure head 42 is terminated.

  That is, the CPU 81 first determines that the light source color has been switched six times in total by switching to R as the light source color, then switching to G and B, then switching to R again, and switching to G and B. Specifically, as shown in FIG. 4, when recording an image for one line, each light source color RGB is repeatedly exposed twice to record an image for one line.

  Next, an example of driving of the exposure head 42 when an image is recorded on the silver halide color photographic light-sensitive material 3 by exposure with the light source color R will be described with reference to flowcharts shown in FIGS.

  First, the CPU 81 determines whether 10 (μs) has elapsed since the switching of the applied voltage (step S101; drive control process). When the CPU 81 determines that 10 (μs) has elapsed (step S101; Yes), the driving of each PLZT chip 421 is started. Here, as shown in FIG. 4, the CPU 81 drives the driver IC 6, that is, the PLZT chip 421 with a delay of 1.0 (μs) (step S <b> 102; drive control step), and ends this process.

  On the other hand, if the CPU 81 determines in step S101 that 10 (μs) has not elapsed (step S101; No), the CPU 81 determines again whether 10 (μs) has elapsed.

  According to the printer 1 described above, the recording head 42 is driven for each PLZT chip 421, so that all of the PLZT elements that perform recording can be used even when the image density in the main scanning direction changes rapidly. It is possible to prevent the number of driven PLZT elements from fluctuating abruptly because the driving is not performed at the same time and the driving start timing is delayed. Therefore, it is possible to suppress the load fluctuation that occurs at the start of driving the PLZT element, and to form a high-quality image with little density unevenness.

  Further, even if a load fluctuation occurs in the PLZT element due to a deviation of 1.0 (μs) or more at the timing of starting driving each PLZT chip 421, the image density unevenness due to the load fluctuation is below the visual recognition level. As a result, density unevenness is not noticeable, and a higher quality image can be formed.

  In general, density unevenness caused by such load fluctuations is likely to occur in an image with a large number of constant density areas such as a design image, and cannot be visually recognized in an image with fine shading. That is, the image unevenness becomes a problem in an image in which the constant density region extends over a certain range.

  Therefore, for example, on the basis of the case where the width of one PLZT chip is simply set as the minimum width, the level of density difference that can be visually recognized is set to about 0.01 as the density difference. This means a density fluctuation (difference) caused by a light quantity fluctuation of about 1.0% in a halftone image having a density of about 1.0.

  When all the PLZT chips are caused to emit light, by setting the timing for starting driving the PLZT chip to 1.0 (μs), the density fluctuation (light quantity fluctuation) compared with the case where one PLZT chip emits light is 1 Within 0.0%. However, it is preferable to further shift this timing in order to obtain a higher quality image.

  In addition, since the applied voltage differs depending on the light source color RGB, the applied voltage can be optimized for each light source color, so that the driving efficiency is optimized, and one line in the sub-scanning direction is achieved. Speeding up can be realized by shortening the time required for recording.

  Then, the switching of the light source color and the start of driving of each PLZT chip 421 are not performed at the same time but at a timing separated by 10 (μs) or more. As a result, it is possible to reliably prevent image quality deterioration due to the influence of noise generated when the applied voltage is switched.

  In addition, the voltage applied to each PLZT chip 421 is increased to a predetermined voltage before the driving of each PLZT chip 421 is started. Thereby, a decrease in density at the start of driving of each PLZT chip 421 can be suppressed, and density unevenness can be prevented more effectively.

  Further, since the light source color is switched at least 6 times within the range where the recording for one pixel is performed in the sub-scanning direction, the recording for one pixel is performed in two steps and the driving of each PLZT chip 421 is started. The shift of the image in the sub-scanning direction caused by shifting the timing can be reduced, and the deterioration of the image quality can be prevented.

  Since the printer 1 is a digital printer for photography of 400 dpi or more, the pixel shift caused by driving each PLZT chip 421 at a different timing by setting the substantial image density to 800 dpi or more is set to 0. Since it can be set to 0065 mm or less, the shift is below a level where it can be visually recognized, and deterioration of image quality can be prevented.

  Further, by using an LED as the light source, the light source color can be switched at high speed, and the speed can be increased.

  Furthermore, in each RGB light source color, the time during which the applied voltage is applied is 500 (μs) or less, so that the writing time for one line is suppressed to 3.0 (ms) or less, and the silver halide color photographic light-sensitive material 3 This can be applied to high-speed printing.

  Note that the CPU 81 (light source color switching means) may switch the light source color a plurality of times for only one of the RGB light source colors. In this case, the recording element is driven a plurality of times for at least one of the light source colors. Therefore, as in the case where the light source color is switched multiple times the number of the light source colors, the recording for one pixel is finely performed in a plurality of times, and the drive start timing of the recording element chip is shifted. The resulting image shift in the sub-scanning direction can be reduced and image quality deterioration can be prevented.

  In the present invention, by using the digital image exposure apparatus having the above-described main structure, even when exposing a large size silver halide color photographic light-sensitive material, pixels up to an area 10 cm away from the exposure center are used. The exposure can be performed with an exposure spot having a substantially circular shape with a pixel ratio (long side / short side) of 1.00 or more and 1.03 or less. As a result, the pixel distortion in the peripheral exposure range is improved, and the character is An image forming method excellent in image blur resistance and color blur resistance could be realized.

  Next, a silver halide color photographic light-sensitive material applied to the image forming method of the present invention and its developing method will be described.

  First, each component of the silver halide color photographic light-sensitive material according to the present invention will be described.

  The silver halide grains in the silver halide emulsion according to the present invention preferably have a silver chloride content of 90 mol% or more, more preferably a silver chloride content of 93 mol% or more, and 95 mol%. More preferably, the above is true. The silver bromide content is preferably 0.1 to 10 mol%, more preferably 0.5 to 8 mol%, and still more preferably 2 to 8 mol%. The silver iodide content is preferably 0.05 to 2 mol%, more preferably 0.05 to 1 mol%.

  In the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used. In this case, the portion containing silver bromide at a high concentration is silver halide. The emulsion grains may be epitaxy-bonded, or may be a so-called core / shell emulsion, or may not have a complete layer but may have only partially different regions. Further, although the composition may change continuously or discontinuously, it is preferable that the silver halide grains have a silver bromide localized phase in at least a part of the outermost shell, in the vicinity of the vertex. It is more preferable to have a silver bromide localized phase.

  The silver bromide localized phase referred to in the present invention is a silver halide phase containing silver bromide having a silver bromide content of at least twice the average silver bromide content of the silver halide grains according to the present invention. The silver halide grains preferably contain silver bromide having a silver bromide content of 3 times or more of the average silver bromide content of the silver halide grains, and preferably contain silver bromide having a silver bromide content of 5 times or more.

  The silver bromide localized phase preferably contains a group 8 metal compound described later. In this case, the Group 8 metal compound used is preferably an iridium complex.

  In the present invention, silver halide grains having at least one silver iodide localized phase inside the grains can also be preferably used. In the present invention, the term “grain interior” refers to a silver halide phase excluding the grain surface in silver halide grains. In the present invention, the silver iodide localized phase is a silver halide phase containing silver iodide having a silver iodide content of at least twice the average silver iodide content of the silver halide grains according to the present invention, It preferably contains silver iodide having a silver iodide content of at least 3 times the average silver iodide content of the silver halide grains, and preferably contains silver iodide having a silver iodide content of 5 times or more. In the present invention, the position of the silver iodide localized phase is preferably 60% or more outside the silver halide volume from the grain center, more preferably 70% or more, and more preferably 80% or more outside. Is most preferred.

  One of the preferred forms of the silver iodide localized phase is that the silver iodide localized phase is present in a layered form inside the silver halide grains (hereinafter also referred to as a silver iodide localized layer). It is also preferable to introduce two or more silver halide localized layers. In that case, at least one layer (hereinafter referred to as sublayer) having a main layer introduced under the above conditions and having a concentration lower than the maximum iodide concentration is more than the main layer. Further, it is preferably introduced near the particle surface. The I concentration of the main layer and sublayer can be arbitrarily selected according to the purpose. From the viewpoint of latent image stability, the main layer preferably has a high density as much as possible, and the sublayer preferably has a lower density than the main layer. In the present invention, another preferred form of the silver iodide localized phase is that the silver iodide localized phase is present in the vicinity of the apex or the ridge line of the silver halide grain, and is used in combination with the above-mentioned silver iodide localized layer. It is also preferable to do.

  When the silver halide emulsion according to the present invention contains silver bromide or silver iodide, the silver bromide content or silver iodide content of the silver halide grains is less than 30%. And is more preferably less than 20%. The lower limit of the coefficient of variation between grains of the silver bromide content is 0.01%.

  The silver bromide content and silver iodide content of the silver halide grains can be determined by the EPMA method (Electron Probe Micro Analyzer method). Specifically, a sample in which silver halide grains are well dispersed so as not to contact each other is prepared, and irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from individual silver halide grains. By determining the characteristic X-ray intensities of silver, bromine and iodine, the silver bromide content and silver iodide content of the individual silver halide grains can be determined.

  By the above method, the silver bromide content and silver iodide content of the silver halide grains determined for each silver halide grain were determined for 300 or more silver halide grains, and the averages were average silver bromide, respectively. The content ratio and the silver iodide content, and the grain-to-grain variation coefficient of the silver bromide content and the silver iodide content of the silver halide grains according to the present invention are determined by the following formula.

Coefficient of variation between grains of silver bromide content = (standard deviation of silver bromide content of silver halide grains) / (average silver bromide content) × 100 (%)
Coefficient of variation between grains of silver iodide content = (standard deviation of silver iodide content of silver halide grains) / (average silver iodide content) × 100 (%)
In the present invention, it is also preferable to use silver halide grains having dislocation lines inside the grains.

  In the present invention, various bromides or iodides can be used to contain silver bromide or silver iodide in the silver halide grains. For example, silver halide fine particles containing silver bromide or silver iodide disclosed in JP-A-2-68538, etc., a method using an aqueous solution of bromide salt or iodide salt such as potassium bromide aqueous solution or potassium iodide Alternatively, a method using a halide ion releasing agent can be arbitrarily used. In the present invention, the silver iodide content, silver bromide content, silver iodide localized phase, silver bromide localized layer, or dislocation line introduction in the silver halide grains, the concentration and amount of these additives, etc. Can be adjusted arbitrarily.

  In order to obtain a silver halide emulsion according to the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given.

  In the present invention, the silver halide grains preferably contain one or more group 8 metal complexes, and contain one or more group 8 metal complex complexes having one or more water ligands or organic ligands. More preferably.

  The group 8 metal complex used in the present invention is preferably a metal complex of iron, iridium, rhodium, osmium, ruthenium, cobalt and platinum. As the metal complex, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, a two-coordinate complex, and the like can be used, and a six-coordinate complex and a four-coordinate complex are preferable. The group 8 metal complex having one or more water ligands and / or organic ligands is more preferably an iridium metal complex.

  In the present invention, the ligand constituting the Group 8 metal complex is a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, or water coordination. Arbitrary, halogen ligands, ammonia, hydroxide, nitrous acid, sulfurous acid, peroxide ligands and organic ligands can be used, but nitrosyl ligands, thionitrosyls. It is preferable to contain one or more ligands selected from a ligand, a cyano ligand, a water ligand, a halogen ligand, and an organic ligand.

  In the present invention, an organic ligand refers to a compound that contains one or more H—C, C—C, or C—N—H bonds and can be coordinated to a metal ion. The organic ligand used in the present invention is selected from pyridine, pyrazine, pyrimidine, pyran, pyridazine, imidazole, thiazole, isothiazole, triazole, pyrazole, furan, furazane, oxazole, isoxazole, thiophene, phenanthroline, bipyridine, and ethylenediamine. It is preferable that the compound is a compound, an ion, or a compound obtained by introducing a substituent into these compounds.

  In the silver halide emulsion according to the present invention, a group 8 metal complex represented by the following general formula (A) can also be preferably used.

Formula (A)
R _n [MX _m Y _6-m ]
In the formula, M represents a metal selected from Group 8 elements of the periodic table, and is iron, cobalt, ruthenium, iridium, rhodium, osmium, or platinum, and more preferably iron, ruthenium, rhodium, iridium, or osmium. R represents an alkali metal, preferably cesium, sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. X and Y represent ligands, such as a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, a halogen ligand, ammonia, water Represents oxide, nitrous acid, sulfurous acid, and peroxide ligands.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When metal ions form a complex, any counter cation such as potassium ions, calcium ions, sodium ions, ammonium ions, etc. can be used. Moreover, when a metal complex is a cation, what is known in this industry, such as a nitrate ion, a halogen ion, a perchlorate ion, can be used as a counter anion.

  In order to contain heavy metal ions in the silver halide emulsion according to the present invention, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, during physical ripening after the formation of silver halide grains. What is necessary is just to add in the arbitrary places of each process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, the heavy metal compound can be dissolved together with the halide salt and continuously added throughout the grain forming process or a part thereof.

The amount of the heavy metal ion added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver halide, and 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol. Mole is more preferred.

  Any shape can be used for the silver halide grains according to the present invention, but a preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, and JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) Volumes of 21, 39 (1973) etc. are used to make particles having shapes such as octahedron, tetrahedron, twenty-fourhedron, dodecahedron, etc. Can also be used. Further, grains having a twin plane other than normal crystals or tabular grains may be used.

  The silver halide grains according to the present invention are preferably grains having a single shape, but two or more monodispersed silver halide emulsions can be added to the same layer.

  The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 0.8, considering other photographic performance such as rapid processability and sensitivity. It is in the range of 2 to 3.0 μm. In particular, when cubic particles are used, it is preferably in the range of 0.1 to 1.2 μm, more preferably 0.15 to 1.0 μm.

  The grain size distribution of the silver halide grains of the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, more preferably 0.10 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a cube or a sphere. To express.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion according to the present invention may be obtained by any of acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.

  Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt solution and a water-soluble halide salt aqueous solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Published Patent No. 2921164 An apparatus for continuously adding a water-soluble silver salt solution and a water-soluble halide salt aqueous solution described in JP-A No. 56-501776, etc. An apparatus that forms grains while maintaining the distance between silver halide grains constant by concentration by a method may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

  The silver halide photographic emulsion according to the present invention is preferably desalted after grain formation. Desalting can be performed, for example, by the method of RD17643, Item II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a noodle water washing method in which gelatin is gelled may be used, and inorganic salts and anionic surfactants may be used. Anionic polymers (eg, polystyrene sulfonic acid) can be used, but precipitation methods using gelatin derivatives and chemically modified gelatin (eg, acylated gelatin, carbamoylated gelatin, etc.) or limitations using membrane separation It is preferable that the filter is desalted by outer filtration.

  As the dispersion medium used in the production of the silver halide emulsion according to the present invention, a compound having a protective colloid property for silver halide grains can be arbitrarily used. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and hydrophilic colloid. Examples of gelatin include alkali-treated gelatin and acid-treated gelatin having a molecular weight of about 100,000, or oxidized gelatin and enzyme-treated gelatin. Can be preferably used. The average molecular weight of gelatin at the time of nucleation of silver halide grains is preferably 10,000 to 70,000, and more preferably 10,000 to 50,000. It is also preferable to use gelatin having a low methionine content during nucleation, and the methionine content per unit mass (gram) of the dispersion medium is preferably 50 μmol or less, more preferably 20 μmol or less. Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, various kinds such as copolymers such as polyvinyl pyrazole A synthetic hydrophilic polymer substance or the like can be used.

  The silver halide emulsion according to the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

  As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer and / or a selenium sensitizer are usable. Agents are preferred.

  Sulfur sensitizers include 1,3-diphenylthiourea, triethylthiourea, thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, thiosulfuric acid Salt, sulfur alone and the like are preferable. In addition, as sulfur simple substance, the alpha-sulfur which belongs to an orthorhombic system is preferable. In addition, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, No. 3,656,955, etc., West German Published Application (OLS) 1,422,869, JP-A-56-24937, 55-45016, etc. are used. be able to.

  As the selenium sensitizer, an unstable selenium compound capable of reacting with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-25832, and 4-109240. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), selenoureas (such as N, N-dimethylselenourea, N, N, N'-triethylseleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'- 4-nitrophenylcarbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamide (eg selenoacetamido, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate, etc.) Phosphates (eg, tri-p-triselenophosphate, etc.), selenides (eg, dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, trifurylphosphine selenide, Trypyridylphosphine selenide). Particularly preferred selenium sensitizers are selenourea, selenoamides, and selenides.

  In the present invention, noble metal salts such as gold, platinum, palladium, iridium and the like described in RD magazine 307, 307105 are preferably used, and in particular, a gold sensitizer is preferably used in combination. Useful gold sensitizers include U.S. Pat. Nos. 2,597,856, 5,049,485, and Japanese Patent Publication No. 44-15748 in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like. And organic gold compounds disclosed in JP-A-1-147537 and 4-70650, gold sulfide, and gold sulfide silver. Further, when performing a sensitization method using a gold complex salt, it is preferable to use a gold ligand such as thiosulfate, thiocyanate, and thioether as an auxiliary agent, and in particular, it is preferable to use thiocyanate. .

  In the above-mentioned various chemical sensitizers, postscript inhibitors, oxidizing agents and the like according to the present invention, JP 2001-318443, JP 2003-29472, JP 2004-37554, 2004-4144, 2004-4446, 2004-4442, 2004-4456, 2004-4458, 2004-4656, 2004-4672, 2003-307803, 2003-287841, 2003 287842, 2003-233146, 2003-172990, 2003-172991, 2003-113193, 2003-113194, 2003-114489, 2002-372765, 2002-296721 No. 2002-278011, No. 2002 No. 268169, No. 2002-244241, No. 2002-259882, No. 2002-258427, No. 2002-268168, No. 2002-268170, No. 2000-193942, No. 2001-75214, No. 2001-75215 2001-75216, 2001-75217, 2001-75218, 2001-100352, 2004-70363, 2004-67695, 2002-131858, 2001-166612, etc. In each publication, European Patent No. 1,094,360, No. 1,388,752, No. 6,686,143, No. 6,322,961, etc. The described compounds and their use techniques can also be preferably used.

The addition amount of the chalcogen sensitizer and gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, and the ripening conditions, but usually 1 × 10 ⁻⁹ per mole of silver halide. It is preferably ˜1 × 10 ⁻⁵ mol. More preferably, it is 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol. Depending on the nature of the sensitizer used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by premixing with a gelatin solution. The method of addition may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

  In the present invention, reduction sensitization may be used, and reducing compounds described in Research Disclosure 307, No. 307105, JP-A-7-78685, and the like may also be used.

  The silver halide emulsion according to the present invention is known for the purpose of preventing fogging that occurs during the preparation process of a silver halide photographic light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging that occurs during development. Antifoggants, oxidizing agents, inhibitors, stabilizers and the like can be used. Examples of preferred compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferred specific compounds. As the compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl) -5-mercapto Compounds such as tetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole, general formula (S) compounds described in JP-A-8-6201, thiosulfonic acid compounds, disulfide compounds, polysulfide compounds and the like are preferable. -145202, 2004-226434, 2004-240182 and the like can be preferably used.

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. A preferable addition amount of these compounds is 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol / mol Ag ×, more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide. For the addition of these compounds, methods commonly used in the art when additives are added to photographic emulsions, coating solutions, preparation solutions and the like can be applied. For example, in the case of a water-soluble compound, an aqueous solution having an appropriate concentration is used. In the case of a compound that is insoluble or sparingly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, ketones It can be dissolved in a solvent that does not adversely affect photographic properties such as esters and amides, and added as a solution.

  In the silver halide color photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-252840, page 30 and The dyes described in JP-A-6-37706 are preferably used, and the infrared absorbing dyes are represented by the general formulas (I), (II), and (III) described in JP-A-1-280750, page 2, lower left column. The compounds have preferred spectral properties and are preferred without affecting the photographic properties of the silver halide photographic emulsion and without contamination by residual colors. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column.

  For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the unprocessed sample of the photosensitive material is 0.7 to 3.0. More preferably 0.

  It is preferable to add a fluorescent brightening agent to the silver halide color photographic light-sensitive material according to the present invention because white background can be improved. Preferred examples of the compound include compounds represented by the general formula (II) described in JP-A-2-232652.

  The silver halide color photographic light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. The pigments IRS-1 to IRS-11 described in pages 6 to 8 of the publication are preferably used. Further, these infrared, red, green and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17.

  These sensitizing dyes may be added at any time from silver halide grain formation to coating solution preparation.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As a coupler used in the silver halide color photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm can be formed by a coupling reaction with an oxidized form of a color developing agent. Any compound can be used, but particularly representative couplers include yellow dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, and magenta dye formation having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm. Examples of couplers include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

  Examples of cyan dye-forming couplers that can be preferably used in the silver halide color photographic light-sensitive material according to the present invention include general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. ) Can be mentioned. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column.

  As a magenta dye-forming coupler which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention, general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, upper right column. ) Can be mentioned. Specific compounds include those described as MC-1 to MC-11 in page 4, lower left column to page 5, upper right column. Among the magenta dye-forming couplers, a coupler represented by the general formula (M-I) described in the upper right column on page 4 of the same publication is preferred. Among them, the RM of the general formula (M-I) is used. A coupler in which is a tertiary alkyl group is particularly preferred because of excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the same publication are preferable because they are excellent in color reproduction from blue to purple and red, and are excellent in detail descriptive power.

  Examples of preferred couplers represented by the above general formula (M-I) are exemplified compounds 1 to 64 described on pages 5 to 9 of JP-A No. 63-253934 and JP-A No. 2-100048. Exemplified compounds M-1 to M-29 described on pages 5 to 6, Exemplified compounds (1) to (36) described on pages 5 to 12 of JP-A-7-175186, JP-A-7-219170 Exemplified compounds M-1 to M-33 described on pages 14 to 22 of the publication, Exemplified compounds M-1 to M-16 described on pages 5 to 9 of JP-A-8-304972, and JP-A-10- Exemplified compounds M-1 to M-26 described on pages 5 to 10 of 207024, Exemplified compounds M-1 to M-36 described on pages 5 to 22 of JP-A-10-207025, US Patent Exemplified compounds described on pages 3 to 6 of No. 5,576,150 -1 to M-24, Exemplified compounds M-1 to M-48 described on pages 3 to 9 of US Pat. No. 5,609,996, 3 of US Pat. No. 5,667,952 Exemplified compounds M-1 to M-23 described on pages 5 to 5, Exemplified compounds M-1 to M-26 described on pages 3 to 6 of US Pat. No. 5,698,386, etc. Can do.

Examples of yellow dye-forming couplers that can be preferably used include couplers represented by general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, a coupler in which RY _{1 in the} general formula [Y-1] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce a yellow color having a preferable color tone. Among these, as particularly preferred compound examples, YC-8, YC-9 described in JP-A-4-114154, page 4, upper left column, and No. described in JP-A-6-67388, pages 13-14 The compound shown by 1)-(47) can be mentioned. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

  When using an oil-in-water emulsion dispersion method to add a coupler or other organic compound used in the silver halide color photographic light-sensitive material according to the present invention, it is usually a water-insoluble high-boiling organic material having a boiling point of 150 ° C. or higher. If necessary, the solvent is dissolved in combination with a low boiling point or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  Examples of the high-boiling organic solvent that can be used to dissolve and disperse the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phosphate. Esters are preferably used. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted on the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until dispersion is added to the coating solution after dispersion and the time from addition to coating after coating is shorter. It is preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas [I] and [II] described on page 3 of JP-A-2-66541, and a general formula [IIIB] described in JP-A-3-1741503. A phenol compound represented by formula (A), an amine compound represented by formula [A] described in JP-A No. 64-90445, a general formula [XII], [XIII], [XIV described in JP-A No. 62-182741 ] And [XV] are particularly preferable for magenta dyes. Further, the compound represented by the general formula [I] described in JP-A-1-196049 and the compound represented by the general formula [II] described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

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

  In the silver halide color photographic light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the photosensitive layer to prevent color turbidity or added to the silver halide emulsion layer. Thus, it is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula [II] described in JP-A-4-133056, compounds II-1 to II-14 described on pages 13 to 14 and compound-1 described on page 17 Is mentioned.

  In the silver halide color photographic light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are those represented by general formula [III-3] described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by [III], UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula [I] described in JP-A-4-16333, JP-A-5-165144 And compounds represented by the general formulas (I) and (II) described in Japanese Patent Publication.

  In the silver halide color photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, gelatin and other polymer graft polymers, other than gelatin. Hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used. The calcium content in gelatin is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less. Further, the content of heavy metals such as zinc, copper, manganese, and iron in gelatin is preferably 10 ppm or less, more preferably 5 ppm or less, and still more preferably 3 ppm or less.

  As these binder hardeners, vinylsulfone type hardeners, chlorotriazine type hardeners, and carboxyl group active hardeners are preferably used alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. Further, in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the physical properties of the surface of the photosensitive material or processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

In the silver halide color photographic material according to the present invention, the total Coating amount of gelatin structure layer is 3 g / m ² or more, preferably 6 g / m ² or less, 3 g / m ² or more, 5 g / m More preferably, it is ² or less. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability, and residual color, the total thickness of the constituent layers is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6.5 μm. It is preferable that The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. Coated silver amount in the present invention is ^{0.3g / m 2 ~0.6g / m 2} .

  Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer. The film pH of the photosensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.

  The silver halide color photographic light-sensitive material according to the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but may form a plurality of color images as necessary. Units may be formed of layers.

  As the support used in the silver halide color photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride. Sheets, polypropylene that may contain a white pigment, polyethylene terephthalate support, baryta paper, and the like can be used. Among these, a reflective support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss is obtained. Also, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, a trace amount of ultramarine, oil-soluble dyes, etc. It is preferable to add a blue tinting agent or a red tinting agent.

  The silver halide color photographic light-sensitive material according to the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic property). One or more subbing layers for improving the properties, dimensional stability, rub resistance, hardness, antihalation properties, frictional properties and / or other properties.

  When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful. As the coating device, a slide coater, a curtain coater, an extrusion coater, or the like can be used.

  In the present invention, in the silver halide color photographic light-sensitive material having the above-described structure, the maximum reflection density after development processing described below has a blue image density of 2.2 or more and a green image density of 2.4 or more. When the digital image exposure apparatus according to the present invention is used, the red image density is 2.3 or more, and the objective effect of the present invention can be sufficiently exhibited, and high quality image quality can be obtained. This is preferable. Further, the maximum reflection density after the development processing may be a blue image density of 2.35 ± 0.05, a green image density of 2.55 ± 0.05, and a red image density of 2.55 ± 0.05. When the digital image exposure apparatus according to the present invention is used, the object and effects of the present invention can be sufficiently exerted, and high quality image quality can be obtained.

  There are no particular restrictions on the maximum reflection density specified above. This can be realized by appropriately selecting the addition amount, halogen composition or grain size of the silver halide emulsion used in each silver halide emulsion photosensitive layer, and the type and addition amount of the coupler.

  In order to form a photographic image using the silver halide color photographic light-sensitive material according to the present invention, an image recorded on the negative is optically imaged on the silver halide photographic light-sensitive material to be printed. Alternatively, after the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and the image is formed on the silver halide photographic material to be printed and printed. Alternatively, printing may be performed by changing the intensity of laser light based on digital information and scanning.

  The silver halide color photographic light-sensitive material according to the present invention is preferably applied to a silver halide color photographic light-sensitive material that does not contain a developing agent, and in particular, a silver halide color photographic light-sensitive material that directly forms an image for viewing. A material is preferred. Examples thereof include color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display, and photosensitive material for color proof, and among them, a silver halide color photographic photosensitive material having a reflective support. It is preferable to apply to.

  In the processing method of the silver halide color photographic light-sensitive material according to the present invention described above, the exposed silver halide color photographic light-sensitive material is subjected to a bleaching step (bleaching solution) following a color developing step (color developing solution). Then, it is dried through a fixing step (fixing solution), a bleach-fixing step (bleaching fixing solution), and a stabilizing step (stabilizing solution). Further, development processing can be continuously performed while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, or the like. The color developer, bleaching solution, bleach-fixing solution, fixing solution, stabilizing solution, and rinsing solution used in the present invention will be described below.

  Preferred examples of the color developing agent used in the color developing solution according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto. It is not something.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Illustrative compounds 5), 6), 7), 8) and 12), among which exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalene disulfonates, p-toluenesulfonates, or free base types (also referred to as free forms). The concentration of the aromatic primary amine developing agent in the working solution is preferably 2 mmol to 200 mmol, more preferably 6 mmol to 100 mmol, and particularly preferably 10 mmol to 40 mmol per liter of the developing solution.

  The color developer used in the present invention preferably contains a preservative to reduce the disappearance of the color developing agent due to oxidation. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Although the hydroxylamine derivative described in 1-187557 etc. can be used, the hydroxylamine derivative represented with the following general formula [A] is especially preferable.

  In the above general formula [A], L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group which may be alkyl-substituted, or an alkyl-substituted group. Represents an ammonio group which may be substituted, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′; , R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

  In the general formula [A], L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, and an ammonio group that may be alkyl-substituted, and preferred examples include a carboxyl group, a sulfo group, a phosphine group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, each of which may be alkyl-substituted. Preferred examples include a carbamoyl group which may be substituted with a group or an alkyl group. As examples of -LA, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group can be mentioned as preferred examples. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. R is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkoxyl group, -O- (B -O) n-R 'and the like. B and R ′ are synonymous with those described in the description of A. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. L and R may be linked to form a ring.

  Although the typical compound example is shown below among the compounds represented by general formula [A], this invention is not limited to these compounds.

  Further, it is also preferable to use sulfite as a preservative, and the concentration thereof is preferably 0.005 to 1.0 mol / L in the color developer for color negative film, and in the color developer for color paper, 0 to 0.1 mol / L is preferable. Examples of sulfites that can be used in the present invention include sodium sulfite, potassium sulfite, and ammonium sulfite.

  In the color developer, in addition to the preservative according to the present invention described above, use of the preservative shown below is not limited. Hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds And condensed amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

  In addition, various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, triethanolamine, and triisopananolamine The alkanolamines described in US Pat. No. 54-3532, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The color developer used in the present invention is preferably 9.0 or more and 13.5 or less, more preferably 9.5 or more and 12.0 or less, and an alkaline agent and a buffer so that the pH value can be maintained. Agents and optionally acids can be included.

  From the viewpoint of maintaining the pH when the color developing solution is prepared, it is preferable to use the buffer shown below. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, and the like can be used. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 10.0 or higher, and even when added to a color developer, they adversely affect photographic performance (capriformation). Etc.) and a preferable buffer from the viewpoint of being inexpensive.

  Exemplary compounds of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) And potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

  These buffers are preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of color developer.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color developer used in the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions during color developer processing. For example, 0. 1 per liter. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developer used in the present invention. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074 Quaternary ammonium salts, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230,796, which are described in JP-A-56-156826 and JP-A-52-43429. No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. Amine compounds described in the report or specification, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. Their concentration is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.05 mol, per liter of the color developer.

  In addition to halogen ions, an optional antifoggant can be added to the color developer as required. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

  In addition, a fluorescent whitening agent can be used in the color developer used in the present invention, if necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available diaminostilbene-based auto-enhancing agent can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK.

  As other bis (triazinylamino) stilbene sulfonic acid compounds, compounds I-1 to I-48 and JP-A-2001-2001 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 are disclosed. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 to 0.1 mol per liter of color developer.

When bromine ions are contained in the color developing solution for color paper, it is preferably 1.0 × 10 ⁻³ mol / liter or less. The color developing solution for color paper preferably contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually used as a by-product in development. Since it is released into the developer, it may not be necessary to add it to the replenisher.

In the present invention, the processing temperature of color development that can be applied by the processing method is preferably 30 to 55 ° C., more preferably 35 to 35 ° C., when the silver halide color photographic light-sensitive material to be developed is color paper. It is 55 degreeC, More preferably, it is 38-45 degreeC. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

  In the present invention, any bleaching agent may be used as the bleaching agent used in the bleaching solution or the bleach-fixing solution. Particularly, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid). Aminopolycarboxylic acids such as cyclohexanediaminetetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates Hydrogen peroxide is preferred.

  Of these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminedisuccinic acid, and iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is preferably 0.01 to 1.0 mol / liter, more preferably 0.05 to 0.50 mol / liter.

  In the bleaching solution or the bleach-fixing solution, various compounds can be used as a bleaching accelerator. For example, a compound having a mercapto group or disulfide bond described in Research Disclosure No. 17129 (July 1978), a thiourea compound, or a halide such as iodine or bromine ion is preferable in terms of excellent bleaching power. .

  In addition, the bleaching solution or the bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide), chloride (for example, potassium chloride) or iodide (for example, ammonium iodide). One or more inorganic acids with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid, succinic acid, maleic acid, glycolic acid Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the fixing solution or the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid Water-soluble silver halide solubilizers such as thioether compounds such as 3,6-dithia-1,8-octanediol and thioureas can be used singly or in combination of two or more. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably from 0.1 to 5.0 mol, more preferably from 0.3 to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9.

  In addition, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain various other kinds of fluorescent whitening agents, antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

  Bleaching solutions, fixing solutions, bleach-fixing solutions are sulphites as preservatives, for example, sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, metabisulfite. Addition of ammonium sulfate or the like is common, but in addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

  Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed. The ammonium cation concentration in the bleaching solution, the fixing solution, and the bleach-fixing solution is preferably 50 mol% or less with respect to the total cations from the viewpoint of workability, but from the viewpoint of processability, the ammonium cation concentration is 50 mol% or more. It is preferable that there is.

The time required for the bleach-fixing step that can be applied to the method for processing a silver halide color photographic light-sensitive material of the present invention is preferably 90 seconds or less, more preferably 45 seconds or less. The time required for the bleach-fixing step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the subsequent rinsing or stabilizing solution, and includes the crossover time therebetween. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Also. The temperature of the bleach-fixing solution is preferably 20 to 70 ° C, and desirably 25 to 50 ° C. Further, the replenishment rate of the bleach-fixing solution is preferably 200 ml / m ² or less, and more preferably ^{20ml / m 2 ~100ml / m 2} .

The replenishment rate of the bleaching treatment solution is preferably 200 ml / m ² or less, and more preferably ^{50ml / m 2 ~200ml / m 2} . The total processing time of the bleaching step is preferably 15 seconds to 90 seconds. The time required for the bleaching step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC. The replenishment rate of the fixing treatment solution is preferably 600 ml / m ² or less, and more preferably ^{20ml / m 2 ~500ml / m 2} . The total processing time of the fixing process is preferably 15 seconds to 90 seconds. The time required for the fixing process here refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC.

  Next, the rinsing or stabilizing process and the treatment liquid used therein will be described.

  Rinsing or stabilizing solution used in the stabilization step includes chelating agents (ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), buffering agents (potassium carbonate, borate, acetate, Phosphates, etc.), antifungal agents (Dearside 702 (made by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), fluorescent brighteners (triazinyl stilbene compounds, etc.) ), Antioxidants (ascorbate, etc.), water-soluble metal salts (zinc salt, magnesium salt, etc.), and the like, which are usually contained in a stable solution, can be used as appropriate.

Furthermore, the rinse or stabilizing solution may contain arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid from the viewpoint of liquid storage stability, and may contain sulfite, bisulfite or metabisulfite. It is also preferable to contain a sulfite. Any organic or inorganic substance may be used as long as it releases sulfite ions, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L or more, more preferably 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol / L in the stabilizing solution. It is added to become L.

  4-10 are preferable and, as for the preferable pH of a stabilization process, More preferably, it is 5-8.

  The temperature of the stabilization step can be variously set depending on the use and characteristics of the silver halide color photographic light-sensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. The time is preferably 5 seconds to 1 minute 45 seconds, more preferably 10 seconds to 1 minute. However, when the silver halide color photographic light-sensitive material is color paper, the time required for the stabilization processing step is 8 to 26 seconds. In addition, when the silver halide color photographic light-sensitive material is a color negative film, the time required for the stabilization process is preferably 10 to 40 seconds.

  A smaller replenishment amount is preferable from the viewpoint of running cost, reduction of discharge amount, handling property, and the like.

A specific preferable replenishing amount is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of silver halide color photographic light-sensitive material, which is brought from the previous bath per unit area. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of} silver halide color photographic light-sensitive material, more preferably 500 ml or less. The replenishment may be performed continuously or intermittently.

  In the treatment method according to the present invention, the structure of the stabilization process using the stabilizing liquid may be composed of one tank or may be composed of two or more layers, preferably two or more tanks. It is preferable to use a multistage countercurrent system constituted by:

  Multi-stage counter-current system is a method of conveying silver halide photographic light-sensitive materials in a stabilizing tank divided into a plurality of stages, while the stabilizing solution overflows into each multi-stage divided stabilizing tank from the downstream to the upstream in the conveying direction of the photosensitive material. It is a system that flows along the road and performs a stabilization process.

  The development processing apparatus used for processing the silver halide color photographic light-sensitive material of the present invention fixes the light-sensitive material to the belt even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank. The endless belt system may be transported in the form of a roller transport, but from the viewpoint of fully exhibiting the object and effects of the present invention, a roller transport that transports a silver halide color photographic light-sensitive material cut into a sheet shape, sandwiched between rollers It is preferable to stay in the type.

  In addition, as the processing tank, the processing tank is formed in a slit shape, and the processing liquid is supplied to the processing tank and the photosensitive material is transported, the spraying method of spraying the processing liquid, and the processing liquid is impregnated. A web system using contact with a carrier, a system using a viscous treatment liquid, or the like can also be used. In the case of processing in large quantities, it is normal that the running processing is performed using an automatic processor. In this case, the replenishing amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishing method. The method described in the published technique 94-16935 is most preferable.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of silver halide emulsion >>
[Preparation of silver halide emulsion (B-1)]
While stirring vigorously using a mixing and stirring apparatus described in JP-A-62-160128, a double ion exchange treated ossein gelatin (calcium content 10 ppm) 2% gelatin aqueous solution kept at 40 ° C. Using the jet method, the following (A1 liquid) and (B1 liquid) were simultaneously added over 17 minutes while controlling pAg = 7.3 and pH = 3.0. Subsequently, the following (A2 solution) and (B2 solution) were simultaneously added over 90 minutes while controlling pAg = 8.0 and pH = 5.5. Furthermore, the following (A3 liquid) and (B3 liquid) were simultaneously added over 15 minutes, controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled and adjusted using sulfuric acid or an aqueous sodium hydroxide solution.

(A1 solution)
Sodium chloride 3.42g
Potassium bromide 0.021g
Water was added to make up to 200 ml.

(A2 liquid)
Sodium chloride 72.0g
K ₂ [IrCl ₆ ] 4.8 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 3.2 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 2.9 × 10 ⁻⁷ mol / mol AgX
K ₂ [IrCl ₅ (thiazole)] 1.6 × 10 ⁻⁸ mol / mol AgX
K ₄ Fe (CN) ₆ 8.0 × 10 ⁻⁶ mol / mol AgX
Potassium bromide 0.44g
Water was added to make 420 ml.

(A3 liquid)
Sodium chloride 30.7g
Potassium bromide 0.63g
Water was added to make 180 ml.

(B1 solution)
Silver nitrate 10g
Water was added to make up to 200 ml.

(B2 liquid)
210g silver nitrate
Water was added to make 420 ml.

(B3 liquid)
90g silver nitrate
Water was added to make 180 ml.

  After completion of the addition, a 15% aqueous solution containing 30 g of chemically modified gelatin (modified rate of 95%) in which the amino group is phenylcarbamoylated is added using the method described in JP-A-5-72658, and then desalted. By mixing with an aqueous solution, a silver halide emulsion (B-1) having an average particle size of 0.59 μm was prepared.

[Preparation of silver halide emulsion (G-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and the amount of K ₄ Fe (CN) ₆ were changed to 2.0 times each, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (G-1) having an average particle size of 0.55 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

[Preparation of silver halide emulsion (GG-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and the amount of K ₄ Fe (CN) ₆ were each changed to 3.8 times, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (GG-1) having an average grain size of 0.43 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

[Preparation of silver halide emulsion (R-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and K ₄ Fe (CN) ₆ are each changed to 4.5 times, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (R-1) having an average grain size of 0.43 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

[Preparation of silver halide emulsion (RR-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and K ₄ Fe (CN) ₆ were each changed to 8.0 times, and (A1 solution), (A2 solution), (A3 solution), (B1 solution), (B2 solution) The silver halide emulsion (RR-1) having an average grain size of 0.40 μm was prepared in the same manner except that the addition time of (B3 solution) was appropriately changed.

  In each silver halide emulsion prepared as described above, cubic silver halide grains accounted for 99% or more of the number of silver halide grains.

<Preparation of blue-sensitive silver halide emulsion>
[Preparation of blue-sensitive silver halide emulsion (B-1a)]
To the silver halide emulsion (B-1) prepared above, the following sensitizing dyes BS-1 and BS-2 were added at 60 ° C., pH 5.8, and pAg 7.5, followed by sodium thiosulfate and trifurylphosphine. Selenide and chloroauric acid were sequentially added to perform spectral and chemical sensitization. After the chemical sensitizer is added and optimally ripened, the compounds (S-1), (S-2), and (S-3) are sequentially added to stop the ripening, and the blue-sensitive silver halide emulsion (B -1a) was obtained.

Sodium thiosulfate 3.9 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.6 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-2) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-3) 2.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 5.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1.3 × 10 ⁻⁴ mol / mol AgX
<< Preparation of green sensitive silver halide emulsion >>
[Preparation of green-sensitive silver halide emulsion (G-1a)]
The following sensitizing dye (GS-1) is added to the silver halide emulsion (G-1) at 60 ° C., pH 5.8, and pAg 7.5, and then sodium thiosulfate, trifurylphosphine selenide and chloride. Gold acid was sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the compound (S-1) was added to stop the ripening to obtain a green sensitive silver halide emulsion (G-1a).

Sensitizing dye: GS-1 5.3 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 3.3 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.2 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.5 × 10 ⁻⁴ mol / mol AgX
[Preparation of green-sensitive silver halide emulsion (GG-1a)]
In the preparation of the green-sensitive silver halide emulsion (G-1a), the silver halide emulsion (GG-1) was replaced with the silver halide emulsion (GG-1) prepared above, and sodium thiosulfate, Silver halide accompanying addition of trifurylphosphine selenide, chloroauric acid, and sensitizing dye (GS-1) as the average grain size of silver halide grains is changed from 0.55 μm to 0.43 μm A green-sensitive silver halide emulsion (GG-1a) was prepared in the same manner except that the addition amount per unit surface area was changed in consideration of the increase in grain surface area.

<< Preparation of red-sensitive silver halide emulsion >>
[Preparation of red-sensitive silver halide emulsion (R-1a)]
The following sensitizing dyes (RS-1) and (RS-2) were added to the silver halide emulsion (R-1) at 60 ° C., pH 5.0, and pAg 7.1, followed by sodium thiosulfate, Furylphosphine selenide and chloroauric acid were sequentially added to give spectral and chemical sensitization. After the chemical sensitizer was added and optimally ripened, compound (S-1) was added to stop ripening, and a red-sensitive silver halide emulsion (R-1a) was prepared.

Sodium thiosulfate 7.2 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 4.8 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Preparation of red-sensitive silver halide emulsion (RR-1a)]
In the preparation of the red-sensitive silver halide emulsion (R-1a), the silver halide emulsion (RR-1) prepared above was used instead of the silver halide emulsion (R-1), and sodium thiosulfate, The addition amount of furylphosphine selenide, chloroauric acid, sensitizing dye (RS-1) and sensitizing dye (RS-2) was changed from 0.43 μm to 0.40 μm in average grain size of silver halide grains. In consideration of the increase in the surface area of the silver halide grains accompanying the formation of the red-sensitive silver halide emulsion (RR-1a), except that each addition amount was changed so that the addition amount per unit surface area was the same. ) Was prepared.

In the preparation of each red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

<< Preparation of silver halide color photographic material >>
[Preparation of Sample 101]
High-density molten polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass is laminated on the photosensitive layer coated surface of paper pulp having a basis weight of 180 g / m ² , and the back surface has a high density. A silver halide color photographic light-sensitive material is formed by subjecting a reflective support laminated with polyethylene to corona discharge treatment, and then providing a gelatin subbing layer and further coating each photographic constituent layer having the constitution shown in Tables 1 and 2. Sample 101 was prepared. In addition, the silver halide emulsion described in the table is represented by a value converted to silver.

In addition, a surfactant (SU-2) is used for preparing a coupler dispersion of each layer, and surfactants (SU-1) and (SU-3) are used as coating aids for adjusting the surface tension of each constituent layer. Was added. Moreover, the antifungal agent (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >. In addition, hardening agents (H-1), (H-2), dyes (AI-1), (AI-2), (AI-3) and additive-1 were added as appropriate.

  Details of each additive used for preparation of the sample 101 are as follows.

Sol-1: tricresyl phosphate Matting agent 1: SiO ₂ (average particle size: 3.0 μm)

<< Evaluation of silver halide color photographic material >>
[Digital exposure]
The sample 101 produced above was exposed to an image pattern of one pixel white line in the main scanning line direction and the other black pattern using the following two exposure apparatuses E1 and E2. For exposure at E1 and E2, a control conversion table (LUT) that associates the image data with the exposure amount control value is created, and the image data of (R, G, B) = (0, 0, 0) is printed. In the above, adjustment was made so that (Y, M, C) = (2.30, 2.50, 2.40).

(Exposure device E1)
The exposure unit shown in FIG. 8 was used as the exposure apparatus E1. The exposure unit 70 includes a red semiconductor laser unit (oscillation wavelength 650 nm) 71R, a green SHG laser unit (oscillation wavelength 544 nm), and a blue SHG laser unit (oscillation wavelength 458 nm) as exposure light sources. Each of them was modulated by an acousto-optic modulator (AOM: Acoustic-Optic Modulator) 73B, 73G, 73R according to the image data. Thereafter, after passing through the light control units 74B, 74G, and 74R, the light is combined by the dichroic mirrors 75B, 75G, or the mirror 75R, reflected by the reflection mirror 76, passed through the cylindrical lens 77, and then directed to the polygon mirror 78. The polygon mirror 78 is rotated in synchronization with the conveyance speed of the photosensitive material 3, and the laser beam reflected here passes through the fθ lens 79 and is then exposed on the photosensitive material 3. Simultaneously with the main scanning on the photosensitive material, the photosensitive material was transported in the direction perpendicular to the main scanning direction (sub scanning). At this time, it was confirmed using a beam monitor that the beam diameter was 100 μm for each of B, G, and R. The exposure time per pixel was approximately 5 × 10 ⁻⁹ seconds. At this time, the distance between the Bolgon laser 78 and the photosensitive material 3 was defined as the optical path length, and the experiment was performed at two points of 40 cm and 70 cm. The resolution was 400 dpi.

(Exposure device E2)
As the exposure apparatus E2, the exposure unit described above with reference to FIGS. 1, these apparatuses include a transport mechanism 2 for transporting the photosensitive material 3 in the transport direction, an exposure mechanism 4 for exposing the photosensitive material 3 in a line shape, a light source color switching unit 5, and the like. The driver IC 6, the conveyance drive unit 7, the light source color switching unit 5 that switches RGB exposure colors (light source colors) based on the image data, the driver IC 6, the exposure control unit 8 that controls the conveyance drive unit 7, and the exposure mechanism 4. It comprises a support member 9 that supports the photosensitive material 3 from below at an exposure location exposed in a line.

As the exposure light source, an LED light source, which is a light source composed of R (red), G (green), and B (blue) light source colors, was used. In the exposure head 42 shown in FIG. 2, an array is formed by arranging a plurality of PLZT chips 421 including a plurality of PLZT elements 425 on a ceramic substrate having slit-like openings, and on both sides of the plurality of PLZT chips 421. A plurality of driver ICs 6 as drive units were arranged. A large number of PLZT elements 425 corresponding to one pixel are arranged in two columns, and each PLZT element 425 is formed in a staggered pattern with one pixel, and one line in the main scanning direction Y in two columns (Odd column, even column). Image was formed. The resolution was 400 dpi. The beam diameter was 100 μm for each of B, G, and R, and the exposure time when the reflection density on the print was Red 0.8, Green 0.8, and Blue 0.8 was approximately 1 × 10 ⁻⁷ seconds per pixel.

  Exposure was performed under the following exposure conditions 1 to 3 using the exposure apparatuses E1 and E2.

  In Table 3, the maximum angle is an angle formed between a perpendicular to the photosensitive material and an exposure beam when the photosensitive material having a width of 10 cm is exposed. The pixel ratio (long side length / short side length) was determined by measuring the short side length and the long side length of the exposure beam at a position 10 cm away from the exposure center.

  Each sample exposed under the above exposure conditions 1 to 3 was subjected to the following development processing.

  An automatic developing machine manufactured by Konica Minolta Photo Imaging Co., Ltd. was modified so that the processing conditions were as follows, and the exposed photosensitive material was processed.

(Processing conditions)
<Processing process><Processingtemperature><Processingtime><Tankcapacity><Replenishmentamount>
Color development 38.0 ° C. 30 seconds 10.2 L 50 ml / m ²
Bleach fixing 38.0 ° C. 30 seconds 10.0 L 37 ml / m ²
Stabilization-1 38.0 ° C 24 seconds 8.0L-
Stabilization-2 38.0 ° C 24 seconds 8.3L-
Stabilization-3 38.0 ° C 24 seconds 8.6L-
Stabilization-4 38.0 ° C 24 seconds 9.0L 150ml / m ²
Drying 60 to 80 ° C. 30 seconds The stabilization process was a multi-stage countercurrent system of stabilization-4 → stabilization-3 → stabilization-2 → stabilization-1.

(Preparation of each treatment solution)
<Color developer: per liter>
Tank liquid Replenisher Diethylene glycol 10.0 g 10.0 g
Polyethylene glycol (average molecular weight 4000) 6.0 g 6.0 g
p-Toluenesulfonic acid 10.0 g 10.0 g
Potassium chloride 4.0 g −
Diethylenetriaminepentaacetic acid 6.0 g 6.0 g
Bis (triazinylamino) stilbene fluorescent whitening agent 1.0 g 1.0 g
N, N-bis (sulfoethyl) hydroxylamine 5.0 g 11.0 g
Lithium hydroxide-3.5g
Potassium carbonate 14.0g 14.0g
Sodium carbonate 10.0g 10.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 2/3 sulfate 6.0 g 12.0 g
1-octane sodium sulfonate 1.0 g 1.0 g
pH 10.00 12.10
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution, sodium hydroxide solution or sulfuric acid.

<Bleach fixer: per liter>
Tank liquid Replenisher Ferric ammonium tetraacetate 0.20 mol 0.37 mol
Ammonium thiosulfate 0.54 mol 1.0 mol
Ammonium sulfite 0.15 mol 0.25 mol
Succinic acid 10.0g 18.0g
N-lauroyl sarcosine sodium 1.5g 1.5g
Nitric acid (67%) 10.0 g 16.0 g
pH 6.0 4.8
Water was added to 1 L, and the pH was adjusted with aqueous ammonia or sulfuric acid.

<Stabilizing liquid: per 1L>
Tank liquid = replenisher 1-hydroxyethylidene-1,1-diphosphonic acid tetrasodium 2.0 g
Ethylenediaminetetraacetic acid disodium 2.0g
o-Phenylphenol 0.1g
Bis (triazinylamino) stilbene fluorescent whitening agent 1.0 g
Sodium sulfite 0.2g
Sodium benzenesulfinate 0.8g
1-octane sodium sulfonate 0.2g
pH 7.5
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or sulfuric acid.

[Evaluation of formed image]
The evaluation image was created by creating image data in which one white line was drawn on a black background in the TIFF format, and each sample 101 was subjected to a visual evaluation using a 20 × magnifier. The visual evaluation was performed under standard observation conditions by requesting 20 engineers who performed a print quality judgment inspection at a developing laboratory, the formed images were evaluated according to the following criteria, and the average value was obtained. If the average value was 3.0 or more, it was judged that the film had practically good characteristics.

5: The boundary line between the white line and the black part is reproduced very clearly. 4: The boundary line between the white line and the black part is reproduced clearly. 3: The boundary line between the white line and the black part is partially at the periphery of the image. Although an unclear part is recognized, it is within a practically acceptable range. 2: The boundary line between the white line and the black part is slightly unclear. 1: The boundary line between the white line and the black part is unclear. As a result, in exposure condition 1, the average value was 1.2, in exposure condition 2, the average value was 2.1, and in exposure condition 3, the average value was 4.0. From this result, it is possible to reduce image blurring and blurring when a thin line is printed by using PLZT and using an exposure device E2 having a pixel ratio of 1.00, compared to the level using the exposure device E1 having a polygon mirror. It can be seen that a good image can be formed.

Example 2
<< Production of Samples 102 to 104 >>
In the preparation of the sample 101 described in Example 1, the silver halide emulsion amount and coupler amount of the first layer (blue sensitive layer), the third layer (green sensitive layer), and the fifth layer (red sensitive layer) were measured. Samples 102 to 104 were prepared in the same manner except that the exposure was performed using the exposure apparatus E2 described in Example 1 so that the maximum density described in Table 4 was obtained.

<Evaluation of text bleeding resistance>
Obtained after printing and developing a character image for the samples 102 to 104 produced above and the sample 101 produced in Example 1 under the exposure conditions 1 to 3 using the exposure apparatuses E1 and E2 described in Example 1. For the character images, the character image quality using a loupe was evaluated by 20 monitors according to the following criteria, and the average evaluation value was obtained. If the average evaluation value was 3.0 or more, it was judged that the film had practically good characteristics.

5: There is black tightening and the character image is reproduced very clearly. 4: Black tightening is present and the character image is reproduced clearly. 3: The character image is partially unclear at the periphery. However, it is within the allowable range for practical use. 2: The black image is poor and the character image is slightly unclear. 1: The black image is poor and the character image is very unclear. Is shown in Table 5.

  As is apparent from the results shown in Table 5, character images are blurred by using PLZT and using an exposure device E2 having a pixel ratio of 1.00, compared to a level using an exposure device E1 having a polygon mirror. It can be seen that the blur is small and a good image can be formed. Among them, as the maximum density, the sample 101 having a maximum cyan density of 2.3, a magenta density of 2.4, and a yellow density of 2.2 or more, or a cyan density of 2.35, a magenta density of 2.55, yellow It can be seen that the effect is more remarkably exhibited in the sample 104 having a concentration of 2.55.

1 is a schematic configuration diagram of a printer according to an embodiment of the present invention. It is a perspective view of a PLZT chip. It is a schematic block diagram of an exposure head. It is a timing chart for demonstrating the drive of an exposure head. It is a figure which shows the transmittance | permeability distribution of the optical shutter of each light source color. 6 is a flowchart illustrating image forming processing for one line by a printer. 3 is a flowchart showing driving of an exposure head in a light source color R. It is a schematic block diagram which shows an example of the exposure apparatus using a polygon mirror.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Printer 2 Conveyance mechanism 3 Photosensitive material 4 Exposure mechanism 42 Exposure head 421 PLZT chip 422 Individual electrode 423 Common electrode 425 PLZT element 5 Light source color switching part 6 Driver IC
7 Transport Drive Unit 8 Exposure Control Unit 81 CPU (Light Source Color Switching Unit, Drive Control Unit)
82 RAM
83 ROM
831 Light source color switching program 832 Drive control program 833 Printing paper conveyance control program

Claims (7)

An image forming method in which a reflection viewing type silver halide color light-sensitive material is exposed using a digital image exposure apparatus, the pixel ratio (long Side / short side) is 1.00 or more and 1.03 or less. The digital image exposure apparatus has an arrayed recording head, and the reflection viewing type silver halide color photosensitive material is moved while moving the recording head and the reflection viewing type silver halide color photosensitive material relative to each other. 2. The image forming method according to claim 1, wherein an image is recorded. The recording head includes a plurality of recording element chips each including a plurality of recording elements, and includes a driving unit that drives the plurality of arranged recording elements, and the driving start timing of the driving unit is set at predetermined intervals. 3. The image forming method according to claim 2, further comprising drive control means for performing shifting control. The image forming method according to claim 3, wherein the driving unit is provided for each of the one or more recording element chips, and the predetermined interval is 1.0 μs or more. 5. The recording head according to claim 2, wherein the recording head has a light source having light source colors of R (red), G (green), and B (blue), and the light source is an LED light source. The image forming method according to item. The maximum reflection density after development processing of the reflection viewing type silver halide color light-sensitive material is such that the blue image density is 2.2 or more, the green image density is 2.4 or more, and the red image density is 2.3 or more. The image forming method according to claim 1, wherein: The reflection reflection type silver halide color light-sensitive material has a maximum reflection density after development of a blue image density of 2.35 ± 0.05, a green image density of 2.55 ± 0.05, and a red image density of 2. 6. The image forming method according to claim 1, wherein the image forming method is .55 ± 0.05.

Images