JP2008250193A - Image forming method using exposure device with micromirror array - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality cinematographic film by an image forming technique by which a uniform gray image can be formed at practical recording speed and a multiple tone using a micromirror device. <P>SOLUTION: An image forming method using a micromirror device including a plurality of micromirrors and a light source which applies light on the device, comprises: exposing an image by projecting reflected light from each micromirror in an effective reflecting state on a silver halide color photographic sensitive material. The photographic sensitive material has red-, green- and blue-sensitive silver halide emulsion layers on transmissive support, at least one of the emulsion layers contains a silver halide emulsion having a silver chloride content of ≥95 mol%, and the emulsion contains at least one metal complex represented by the general formula (D1): [M<SP>D1</SP>X<SP>D1</SP><SB>n</SB>L<SP>D1</SP><SB>(6-n)</SB>]<SP>m</SP>and at least one metal complex represented by the general formula (D2): [IrX<SP>D2</SP><SB>n</SB>L<SP>D2</SP><SB>(6-n)</SB>]<SP>m</SP>. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an image forming technique using a photosensitive material suitable for using a micromirror device in which a plurality of micromirrors are arranged in a line and exposing an image with light from each micromirror.

  Recently, a micromirror type spatial light modulator has been proposed in which mirrors with extremely small sizes (hereinafter referred to as micromirrors) are arranged in a line or matrix, and the incident light is changed by controlling the tilt angle of each micromirror. . Examples of the micromirror spatial light modulator include a digital micromirror device (DMD) that tilts the micromirror with electrostatic force, and a piezoelectric micromirror device (AMA) that tilts the micromirror with a small piezoelectric element. Since these micromirror devices have an image forming function, they are considered to be used in projectors and printers. The principle and application examples of the digital micromirror device are described in Non-Patent Document 1, for example.

  For example, in a digital micromirror device, a plurality of micromirrors are arranged in a line. Each micromirror is in a horizontal state when the power is off, and in accordance with the value of 1-bit mirror drive data written in the memory cell, an effective reflection state inclined by + θ with respect to the vertical line, and − It shifts to the ineffective reflection state inclined by θ.

  In a micromirror printer using this digital micromirror device, illumination light is constantly irradiated onto the digital micromirror device from an oblique direction. When the micromirror is set in the effective reflection state, the reflected light enters the image forming optical path. A projection lens is disposed in the image forming optical path, and one line of spot light is projected onto the photosensitive material or the screen. When the micromirror is set in the invalid reflection state, the reflected spot light enters the removal optical path, is absorbed by, for example, a light absorbing member provided in the removal optical path, and is not used for image formation.

  As described above, since the micromirror device is controlled by the binary state of whether or not the spot light is projected onto the photosensitive material, when recording an image with multiple gradations, the micromirror is in an effective reflection state. The time to be controlled. A well-known pulse width modulation is used for this control. In the pulse width modulation, for example, the exposure amount can be changed stepwise by sequentially halving the timing of switching the micromirror to the effective reflection state or the invalid reflection state while exposing one line. it can.

  By the way, when the micromirror of the micromirror device is displaced from either the effective reflection state or the ineffective reflection state to the other state, a finite response time (displacement period) is required. For this reason, when the interval for switching the reflection state of the micromirror is very short, the micromirror cannot respond completely.

  For example, if 256 pixels of one pixel are recorded with one micromirror by 8-bit pulse width modulation, the pixel density is 600 dpi, and the recording speed is 1.75 inch / sec, the digital micromirror Each micromirror of the apparatus requires a response time of about 1 μs, but since the response time of the digital micromirror apparatus is about 15 μs, such recording is difficult to realize. That is, it is impossible to finely control the gradation level, and a relatively large number of gradations cannot be recorded. As a method for solving such a problem, a density gradation printing method using a spatial light modulator is provided (for example, see Patent Document 1).

  According to the method described in Patent Document 1, a large number of micromirror arrays in which a large number of micromirrors are arranged in a line are arranged, and multiple exposure is performed a plurality of times for each line by these micromirror arrays. As a result, the response speed required for the digital micromirror device is reduced (response time is lengthened). For example, when 64 micromirror arrays are used, if applied to the above example, the response time required for the digital micromirror device is about 60 μsec, and recording at 256 gradation levels is possible.

  However, in the method described above, if a higher recording speed or a larger number of gradations is obtained, the number of multiple exposures must be increased. For this reason, it is necessary to provide a large number of micromirror devices or micromirror arrays of micromirror devices, which causes a problem of increasing costs. Therefore, it is difficult to reduce the manufacturing cost and cope with higher recording speed and higher gradation recording. In addition, when three-color exposure is performed in red, green, and blue, if the three-color exposure time is equally allocated to one exposure time by one micromirror array, the required micromirror device is provided. The response speed is tripled (response time is 1/3). When recording is performed using 64 micromirror arrays as described above, a response time of 20 μsec is required. Therefore, the minimum exposure time that can be controlled by pulse width modulation becomes very short, and a higher number of gradations cannot be desired. Note that if the conveyance speed of the photosensitive material is set low, the required response time can be lengthened. However, in this case, there is a problem that the recording speed is lowered and is not suitable for practical use.

  As an exposure method that solves the above problems and can record a practical recording speed and a multi-tone image using a micromirror device with a small number of micromirror arrays, for example, Patent Document 2 discloses an effective reflection state. There has been proposed a method in which exposure is performed by a printer having a light source modulation means for changing the lighting time of a light source that irradiates a held micromirror.

  However, there is a problem that when a gray image is created with these apparatuses and a normal movie film, a uniform gray image cannot be obtained because the color is different between the central portion and the peripheral portion of the film.

On the other hand, in order to provide high illuminance digital exposure appropriateness using a laser as a light source, for example, Patent Document 3 discloses the use of the novel dopant of the present invention. However, high illuminance digital optimization is achieved here by using together with Se sensitizing compounds, and the above-mentioned problem is not mentioned at all.
JP-A-7-131648 Japanese Patent Laid-Open No. 9-318892 JP 2005-292822 A Monthly magazine "O plus E", published by New Technology Communications, October 1994, pages 90-94

  The present invention solves the above-mentioned conventional problems and develops an image forming technique capable of forming a uniform gray image at a practical recording speed and multi-tone using a micromirror device of a micromirror array, thereby producing a high-quality movie. An object is to provide a film.

  Means for solving the above problems are as follows.

  (1) It has at least one micromirror array in which a plurality of micromirrors are arranged in a line, and each micromirror can be displaced between an effective reflection state and an invalid reflection state according to 1-bit mirror drive data. A printer having a micromirror device and a light source for irradiating light to the micromirror device, and projecting the reflected light from each micromirror in an effective reflection state onto a photosensitive material and a silver halide color In an image forming method using a photographic light-sensitive material, the silver halide color photographic light-sensitive material is formed on a transmissive support on a red-sensitive silver halide milk layer, a green-sensitive silver halide milk layer, and a blue-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material for cinema having at least one silver halide emulsion layer having a silver chloride content of 95 mol% or more A silver halide color photographic light-sensitive material for movies containing a silver halide emulsion, and the silver halide emulsion contains at least one metal complex represented by the following general formula (D1) and general formula (D2): An image forming method characterized by that.

General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
(In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, X ^D1 represents a halogen ion, and L ^D1 is an arbitrary different from X ^D1 Wherein n represents 3, 4, 5 or 6, and m represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+, where A plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different, provided that the metal complex represented by the general formula (D1) is used as a ligand. (There is no or no CN ion.)
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
(In the general formula (D2), X ^D2 represents a halogen ion or a pseudo-halogen ion (excluding a cyanate ion), and L ^D2 represents an arbitrary ligand different from X ^D2. N is 3, 4 Or 5, wherein m is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2 may be the same or different from each other. Well, when there are multiple ^LD2s , these may be the same or different.)
(2) The metal complex represented by the general formula (D1) is contained in silver halide grains in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol per mol of silver (1) The image forming method described in 1.

  (3) The image forming method according to (1) or (2), wherein the metal complex represented by the general formula (D1) is a metal complex represented by the following general formula (D1A).

General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
(In the general formula (D1A), M ^D1A represents Re, Ru, Os or Rh, X ^D1A represents a halogen ion, L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, M ^{When D1A} is Rh, it represents H ₂ O, OH or O. n represents 3, 4, 5 or 6, m is the charge of the metal complex, and 4-, 3-, 2-, 1-, Represents 0 or 1+, wherein a plurality of X ^D1A may be the same as or different from each other, and when a plurality of L ^D1A are present, they may be the same or different;
(4) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2A), described in any one of (1) to (3) Image forming method.

General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
(In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), L ^D2A represents an arbitrary inorganic ligand different from X ^D2A , n is 3, 4 or 5 and m is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0, or 1+, where a plurality of X ^D2A may be the same or different from each other And when there are a plurality of L ^D2A , these may be the same or different.)
(5) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2B), (1) to (3) Image forming method.

General formula (D2B)
^{_{[IrX D2B n L D2B (6}} -n)] m
(In the general formula (D2B), X ^D2B represents a halogen ion or a pseudo-halogen ion (excluding a cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or a base thereof. Represents a ligand in which a carbon or hydrogen atom in a part of the structure is replaced with another atom or atomic group, n represents 3, 4 or 5, m represents the charge of the metal complex, and 5-4 -, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2Bs may be the same as or different from each other, and when a plurality of L ^D2Bs are present, they may be the same or different. .)
(6) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2C), described in any one of (1) to (3) Image forming method.

General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
(In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand, and has at least one nitrogen atom in the ring skeleton. Represents a ligand containing at least one sulfur atom, and may have an optional substituent on a carbon atom in the ring skeleton, n represents 3, 4 or 5, and m represents the charge of the metal complex. 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2Cs may be the same as or different from each other, and when a plurality of L ^D2Cs are present, May be the same or different.)
(7) Any one of (1) to (6), wherein the light source of the printer is provided with light source modulation means for changing a lighting time of a light source that irradiates a micromirror held in an effective reflection state. The image forming method according to item.

  According to the image forming method of the present invention, a high-quality image having a uniform gray image can be obtained using a printer incorporating a micromirror array and a color photosensitive material.

  A specific embodiment of the printer used in the present invention will be described. FIG. 2 shows a digital micromirror device used as a micromirror device. The digital micromirror device 10 is provided with a single micromirror array 11, and the micromirror array 11 is composed of a large number of micromirrors 12 arranged in a line.

  As shown in FIG. 3, each micromirror 12 is held by a static RAM (SRAM) 14 in a swingable manner via a post 13 located at the center thereof. Each micromirror 12 has a rectangular shape with a side length of 16 μm, for example, and is made of a metal thin film such as aluminum having conductivity.

  Address electrodes 15 and 16 are formed on both sides of the post 13, and the micromirror 12 is inclined by electrostatic force generated between the address electrodes 15 and 16 and the micromirror 12. That is, the micro mirror 12 is tilted so that one of the corners 12 a and 12 b on the diagonal passing through the post 13 and the address electrodes 15 and 16 contacts the silicon substrate of the SRAM 14. Actually, two corners on the other diagonal line are held hollow by a pair of support posts via a threaded hinge. Each element such as the micromirror 12 and the post 13 is manufactured by a well-known integration technique.

  As shown in FIG. 4, each micromirror 12 is disposed on each memory cell 14 a of the SRAM 14. The memory cell 14a is composed of a flip-flop having two transistors and stores 1-bit data. In the flip-flop, one transistor is ON and the other transistor is OFF in the driving state. This ON / OFF state is reversed by a pulse (input data).

  Address electrodes 15 and 16 are connected to each transistor constituting the flip-flop. Therefore, one of the address electrodes 15 and 16 is “+” and the other is “−”, which is “+” depends on the mirror drive data written in the memory cell 14a. When a predetermined bias voltage is applied to the micromirror 12, the micromirror 12 tilts to one of the two due to the electrostatic force generated between the address electrodes 15 and 16 of the micromirror 12.

  When the power supply is off, both the two transistors are off, so that no voltage is applied to the address electrodes 15 and 16. In addition, no bias voltage is applied to the micromirror 12. For this reason, the micromirror 12 is in a horizontal state as shown in FIG. Even when the mirror drive data is written in the memory cell 14a, the state is horizontal when no bias voltage is applied to the micromirror 12.

  When mirror drive data of “0” is written in the memory cell 14a of the SRAM 14, the address electrode 15 becomes “+” and the address electrode 16 becomes “−”. When a “+” bias voltage is applied to the micromirror 12, a repulsive force is generated between the address electrode 15 and the micromirror 12, and an attractive force is generated between the address electrode 16 and the micromirror 12. Due to these electrostatic forces, as shown in FIG. 4B, the micromirror 12 is tilted until the corner 12b contacts the silicon substrate. The inclination angle of the micromirror 12 at this time is −θ.

  When mirror drive data “1” is written in the memory cell 14 a of the SRAM 14, the address electrode 15 becomes “−” and the address electrode 16 becomes “+”. In this case, the micromirror 12 is tilted by + θ as shown in FIG. Therefore, the micromirror 12 is tilted between + θ and −θ according to the value of the mirror drive data.

  The micromirror 12 has a horizontal state and two inclined states. Two inclined states are used during image formation, and spot light from the micromirror 12 is extracted in one of the inclined states. Form an image. For example, when the micromirror 12 is + θ, the spot light reflected by the micromirror 12 is put into the image forming optical path and projected onto the photosensitive material. At -θ, spot light is unnecessary, so it is put in the removal optical path. In this case, when it is + θ, the reflected light is in an effective reflection state used for image formation. When the micromirror 12 is −θ, the reflected light is in an invalid reflection state where it is not used for image formation.

  In addition, since one micromirror 12 records one pixel, both the continuous time and the number of times that the micromirror 12 is in the effective reflection state, or both the time and the number of times that the micromirror 12 is in the effective reflection state by pulse width modulation or the like By changing, the gradation of the pixel can be expressed. For example, the number of “1” mirror drive data corresponding to the image data is generated and the serial mirror drive data is sequentially written in the memory cell 14a, whereby the number of effective reflection states can be changed. In addition, the time during which the mirror drive data is rewritten can be changed to adjust the time during which the effective reflection state is set. The response time during which the micromirror 12 is displaced from either the effective reflection state or the ineffective reflection state to the other state is about 15 μsec.

  FIG. 5 shows a digital color printer using the digital micromirror device 10 described above. As a light source for illuminating the digital micromirror device 10, a red LED device 20 in which a large number of red LEDs are formed in a line shape on a substrate, and a green LED device 21 and a blue LED device 22 having the same configuration are used. By controlling the lighting time of each of these LED devices and the time during which the micromirror 12 is in the effective reflection state, it is possible to control the exposure time even shorter than the minimum exposure time that can be controlled by the micromirror 12. It is said. The LED has a short response time from the light-off state to the light-on state or from the light-off state to the light-on state, for example, about 1/10 of that of the micromirror 12, so that it is effective for controlling the light-on and light-off in a short time. .

  Red light from the red LED device 20 passes through the dichroic mirror 24 that reflects green light and the dichroic mirror 25 that reflects blue light, and is diffused by the diffusion plate 26. The diffused red light is converted into parallel light by the lens 27 and then enters the digital micromirror device 10. Green light from the green LED device 21 is reflected by the dichroic mirror 24 and then enters the digital micromirror device 10 through the dichroic mirror 25, the diffusion plate 26, and the lens 27. Blue light from the blue LED device 22 is reflected by the dichroic mirror 25 and enters the digital micromirror device 10. Each color light uniformly irradiates the micromirror array 11 of the digital micromirror device 10.

  The LED driver 28 is controlled by a lighting control circuit 29 as a light source modulation means, and switches the red LED device 20, the green LED device 21, and the blue LED device 22 that are turned on each time a switching signal is input. The LED driver 28 turns on only the red LED device 20 in the red exposure sequence, turns on only the green LED device 21 in the green exposure sequence, and turns on only the blue LED device 22 in the blue exposure sequence.

  The controller 30 as the exposure sequence control means controls each part and sequentially performs the red, green, and blue exposure sequences. Further, the controller 30 sends a timing pulse as a write synchronization signal to the data write control circuit 35 in order to adjust the exposure amount of each pixel on the photographic paper 41 by a known pulse width modulation method. For example, when recording with 32 gradations, the controller 30 generates five timing pulses from the first to the fifth during each exposure sequence.

  The timing pulse generation interval is sequentially halved and gradually shortened, and is 1/2, 1/4, 1/8, and 1/16 of the time T of the exposure sequence from the time when the first timing pulse is generated. The second and subsequent timing pulses are generated in order at intervals, and the first timing pulse of the next exposure sequence is generated when 1/16 · T has elapsed after the generation of the last timing pulse. In this way, the sub-sequence is between the generated timing pulse and the timing pulse, and five sub-sequences are performed during each exposure sequence.

  The timing pulse is also sent to the lighting control circuit 29 in order to perform lighting control of the LED devices 20 to 22 performed during the exposure sequence of each color. The lighting control circuit 29 controls the lighting or extinguishing of the LED device by sending and stopping the LED lighting signal based on this timing pulse.

  Specifically, the period from the time when the first timing pulse is generated to the time when the fifth timing pulse is generated, that is, during execution of the first to fourth sub-sequences, corresponds to the exposure sequence being executed. In the final fifth sub-sequence, a predetermined time (in this example, 1/32 · T) is maintained while the micromirror 12 is in an effective reflection state in the last fifth sub-sequence. Only the LED device of the color corresponding to the exposure sequence being executed is turned on. The lighting control circuit 29 counts the number of timing pulses to detect completion of exposure for one color, and sends a switching signal to the LED driver 28 every time one color is recorded for one line.

  In the red image memory 31, the green image memory 32, and the blue image memory 33, three color image data (digital image data) for one frame is written, and one line to be recorded from the image memory corresponding to the color to be exposed. Minute image data is read out. For example, in the red exposure sequence, one line of red image data is read from the red image memory 31 and sent to the data conversion circuit 34, where each red image data is converted into mirror drive data. The data write control circuit 35 writes mirror drive data to the SRAM 14 of the digital micromirror device 10 in synchronization with the timing pulse.

  When the micromirror 12 is tilted by −θ by the mirror drive data of “0”, the micromirror 12 enters an invalid reflection state, and the reflected light enters the removal optical path 37. Since this reflected light is unnecessary, it is absorbed by the light absorbing plate 38.

  When the mirror drive data is “1”, the micromirror 12 is in an effective reflection state inclined by + θ, and the spot-like reflected light enters the image forming optical path 39. A projection lens 40 is disposed in the image forming optical path 39, and the spot light for one line is projected onto a photosensitive material, for example, a well-known silver salt type photographic paper 41. As shown in FIG. 6, the micromirror array 11 of the digital micromirror device 10 is arranged such that the micromirrors 12 are arranged in the main scanning direction (direction perpendicular to the transport direction). The light reflected by each micromirror 12 in the effective reflection state passes through the projection lens 40 and is projected in a line shape in the width direction of the photographic paper 41, and one pixel PS is recorded by one micromirror 12.

  In FIG. 5, the photographic paper 41 is nipped by the conveyance roller pair 43, is intermittently pulled out from the supply roll 44 line by line in the conveyance direction (sub-scanning direction), and is sent to the processor 45. While the photographic paper 41 is stopped, an image of three colors is recorded for one line. Then, the color image for one frame is recorded by sequentially feeding the photographic paper 41. The rotation of the pulse motor 46 for rotating the conveyance roller pair 43 is controlled by the controller 30 via the driver 47. The photographic paper 41 on which the image is recorded is developed by the processor 45. Reference numeral 49 denotes a mask plate that divides the exposure range.

  Next, the operation of the digital color printer will be described with reference to FIGS. FIG. 1 shows an example of the timing pulse, the operating state of the micromirror 12 and the lighting state of the red LED device 20 in one red exposure sequence. FIG. 7 shows the relationship between the motor driving pulse when one line is recorded and the lighting states of the LED devices 20 to 22.

  When the power is turned on, the controller 30 instructs the data write control circuit 35 to clear the digital micromirror device 10. The data writing control circuit 35 writes “0” to the SRAM 14 of the digital micromirror device 10 and tilts each micromirror 12 by −θ to an invalid reflection state as shown in FIG.

  Next, the controller 30 continuously supplies motor drive pulses to the motor driver 47 and conveys them until the recording start position (first line) of the photographic paper 41 reaches the projection position by the micromirror array 11. When the first line of the photographic paper 41 reaches the projection position, the controller 30 stops the conveyance of the photographic paper 41 and then starts the red exposure sequence. First, the first sub-sequence of the red exposure sequence is started, and the red image data of the first line is read from the red image memory 31 and sent to the data conversion circuit 34. The data conversion circuit 34 converts each red image data into, for example, 5-bit mirror drive data in order to perform pulse width modulation. This mirror drive data includes the number “1” corresponding to the value of the image data, and if each image data represents the gradation of the corresponding pixel with 5 bits, the image data and the mirror drive data The contents of are the same. When the bit numbers of the image data and the mirror drive data are different, the data converted by the data conversion circuit 34 becomes the mirror drive data.

  The data conversion circuit 34 extracts the most significant bit of the mirror drive data for each pixel PS and sends it to the data write control circuit 35. Then, in synchronization with the first timing pulse, mirror drive data for one line is written in each memory cell 14a of the digital micromirror device 10.

  The micromirror 12 maintains the invalid reflection state when the mirror drive data of “0” is given. Further, when the mirror drive data of “1” is given, the micro mirror 12 tilts from the invalid reflection state to the effective reflection state.

  On the other hand, when receiving the first timing pulse, the lighting control circuit 29 sends a switching signal to the LED driver 28, designates the red LED device 20, and sends an LED lighting signal to the LED driver 28. Thereby, the red LED device 20 is turned on, and the entire surface of the digital micromirror device 10 is illuminated with red light.

  The red light incident on each micromirror 12 in the effective reflection state is reflected toward the image forming optical path 39 as spot light. The red spot light is projected onto the photographic paper 41 by the projection lens 40 that is in focus. Thereby, red spot light for one line is projected at the position of the first line of the photographic paper 41, and red sub-exposure is performed by the first sub-sequence. This exposure is performed until the second timing pulse is generated. As a result, during this first sub-sequence, red exposure of time 1/2 · T is performed by each micromirror 12 in the effective reflection state.

  Next, the data conversion circuit 34 extracts the second most significant bit of each mirror drive data and sends it to the data write control circuit 35. The controller 30 generates the second timing pulse when time 1/2 · T has elapsed from the time when the first timing pulse was generated. The data write control circuit 35 writes mirror drive data for one line to the digital micromirror device 10 by the second timing pulse. At this point, the first subsequence is finished and the second subsequence is started.

  The micromirrors 12 of the first micromirror array 11 to which the mirror driving data “0” is given by the second timing pulse are displaced from the effective reflection state to the invalid reflection state, or maintain the invalid reflection state. Further, the micromirror 12 to which the mirror drive data of “1” is given is displaced from the invalid reflection state to the effective reflection state or maintains the effective reflection state. Since the lighting control circuit 29 continuously sends the LED lighting signal to the LED driver 28, the digital micromirror device 10 is irradiated with red light even during the second sub-sequence, and is in an effective reflection state. The second red sub-exposure is performed at the position of the first line of the photographic paper 41 by the red spot light from the micromirror 12. In the second sub-sequence, red exposure of time ¼ · T is performed by each micromirror 12 in the effective reflection state.

  When time 1/4 · T has elapsed since the second timing pulse is generated, the third timing pulse is generated, the second sub-sequence is completed, and the third sub-sequence is started. In the third sub-sequence, each micromirror 12 is driven by the upper third bit of each mirror drive data. Then, when time 1/8 · T has elapsed since the generation of the third timing pulse, the fourth timing pulse is generated, the fourth sub-sequence is started, and the upper 4 bits of each mirror drive data Each micromirror 12 is driven by the eyes. Furthermore, the fifth timing pulse is generated when the time 1/16 · T has elapsed since the fourth timing pulse was generated.

  In this way, in the first to fourth sub-sequences in the red exposure sequence, the effective reflection state of each micromirror 12 according to the mirror drive data from the upper 1st bit to the upper 4th bit of the mirror drive data, respectively. Are controlled to exposure times of 1 / 2.multidot.T, 1 / 4.multidot.T, 1 / 8.multidot.T, 1 / 16.multidot.T, and by combining these times, each micromirror 12 is controlled. The exposure amount of the corresponding pixel PS is adjusted in 16 steps.

  When the fifth timing pulse is generated and the fifth sub-sequence is reached, the lighting control circuit 29 once stops sending the LED lighting signal. Thereby, the red LED device 20 is turned off. The write control circuit 35 writes the lower first bit (least significant bit) of each mirror drive data to the digital micromirror device 10. As a result, the micromirror 12 corresponding to the image data that needs to be subjected to red exposure at time 1/32 · T is in the effective reflection state during the fifth sub-sequence.

  When a predetermined time elapses after the fifth timing pulse is input, the lighting control circuit 29 sends an LED lighting signal to the LED driver 28 for a time 1/32 · T. At this time, the LED lighting signal takes into account the response time of the micromirror 12, and after the fifth timing pulse is generated, the micromirror 12 that has been in the invalid reflection state according to the mirror drive data of “1” During the period when the micromirror 12 is in the fully effective reflection state, it is generated with a delay necessary for reaching the fully effective reflection state, that is, the response time or more. The LED device 20 is turned on.

  As a result, in the fifth sub-sequence, the red spot light is reflected toward the image forming optical path 39 from the micromirror 12 which is in the effective reflection state for the time 1/32 · T, and is photographic paper 41 via the projection lens 40. Projected on. Thereby, red sub-exposure is performed at time 1/32 · T.

  By the way, when the recording speed is increased or the number of gradations that can be recorded is increased, the subsequence time (subexposure time) at that time is shortened when a small exposure amount is given by pulse width modulation. Therefore, the response time required for the micromirror is shortened. However, since the response time of the micromirror 12 is determined, there is a limit to the minimum value of the exposure time that can be adjusted by driving the micromirror 12. For example, if the minimum exposure time that can be adjusted by the response time of the micromirror 12 in this digital color printer is 1/16 · T, the exposure of the time 1/32 · T is controlled by driving the micromirror 12. I can't.

  However, in this digital color printer, it is necessary to perform the sub-exposure for a time (1/16 · T) within a range in which the micromirror 12 can respond to the sub-exposure of time 1/32 · T as described above. Since the micromirror 12 corresponding to the pixel PS is in the effective reflection state and the red LED device 20 is lit for the time 1/32 · T during that time, the response time is not limited by the response time of the micromirror 12. An exposure time shorter than the minimum exposure time corresponding to the time can be controlled. As a result, each pixel PS of the first line of the photographic paper 41 is recorded with 32 gradations with the red exposure amount adjusted in 32 steps.

  When the red exposure sequence ends, the controller 30 starts the green exposure sequence. First, the controller 30 starts the first sub-sequence of the green exposure sequence, reads the green image data of the first line from the green image memory 32, and sends it to the data conversion circuit 34. The data conversion circuit 34 converts each line of green image data into 5-bit mirror drive data.

  Thereafter, the most significant bit of each mirror drive data is taken out, sent to the data write control circuit 35, and written into the memory cell 14a with the first timing pulse. The inclination of each micromirror 12 changes according to the corresponding mirror drive data. Further, when the first timing pulse is generated, the lighting control circuit 29 sends a switching signal to the LED driver 28 to designate the green LED device 20 and send an LED lighting signal to light the green LED device 21. .

  Each micromirror 12 in the effective reflection state reflects the green spot light toward the photographic paper 41. Thereby, green light is exposed at the position of the first line of the photographic paper 41. Thereafter, similarly to red exposure, the second to fourth sub-sequences using green light are performed, and three sub-exposures are performed. Next, when the fifth timing pulse is generated and the fifth sub-sequence is started, the green LED device 21 is turned off once, and each micro mirror 12 is driven by the lower first bit of the mirror drive data. Is done. During this time, the green LED device 21 is turned on for a time 1/32 · T. Thus, each pixel PS on the first line is exposed with the green exposure amount adjusted in 32 steps.

  When the green exposure sequence is completed, the blue exposure sequence is started, and blue exposure is performed at the position of the first line of the photographic paper 41 based on the blue image data of the first line in the same procedure as described above. When the blue exposure sequence ends, one motor drive pulse is sent to the motor driver 47, the pulse motor 46 rotates, and the photographic paper 41 is fed by one line. Thereafter, the red, green, and blue sequences are sequentially performed in the same manner as described above, and the second line is recorded in three colors. Further, every time the photographic paper 41 is fed by one line, an exposure sequence of three colors is sequentially performed, and the third and subsequent lines are sequentially recorded to record a color image for one frame.

  In this way, a full color image is recorded as a latent image on the photographic paper 41 line by line. The recorded portions are sequentially sent to the processor 45, and are subjected to photographic development as is well known, whereby a color image for one frame is developed.

  As described above, since the exposure time shorter than the minimum exposure time limited by the response time of the micromirror can be controlled, multiple gradations can be recorded at high speed with a small number of micromirror arrays. Conversely, the number of gradations can be increased without slowing the recording speed.

  When using positive-positive printing paper, the digital micromirror device 10 is driven using image data of a positive image. When using normal photographic paper that is negative / positive-inverted, image data that is inverted to a negative image is used.

  8 to 10 show examples in which two micromirror arrays are provided. In addition, parts other than those described below are the same as those in the above-described embodiment, and components having substantially the same functions will be described with the same reference numerals.

  As shown in FIG. 8, in the digital micromirror device 50, two first and second micromirror arrays 51 and 52 are arranged at regular intervals. Each of the micromirror arrays 51 and 52 includes a large number of minute micromirrors 12 arranged in a line. These micromirrors 12 are arranged in a matrix in which the horizontal and vertical directions are aligned, but the second micromirror array 52 is displaced in the line direction by half the pitch of the micromirrors 12 with respect to the first micromirror array 51. They may be arranged in a staggered matrix. The light reflected from the respective micromirror arrays 51 and 52 toward the image forming optical path 39 is projected onto the photographic paper 41. Thus, one line by the first micromirror array 51 and one line by the second micromirror array 52 are projected onto the photographic paper 41, respectively.

  The data conversion circuit 34 reads the image data for two continuous lines from any one of the image memories 31 to 33 corresponding to the color to be exposed, converts them into 5-bit mirror drive data, and writes the data. This is sent to the control circuit 35.

  For example, in the red exposure sequence, red image data of the Mth line and the (M−1) th line are read and converted into mirror drive data. In this conversion, the data conversion circuit 34 sets the upper 1st bit to the upper 4th bit of the mirror drive data to “1” or “0” corresponding to the image data for the Mth line, and the least significant bit. Is set to “0” regardless of the size of the image data. For the (M−1) th line, the upper 1st bit to the upper 4th bit of the mirror drive data are set to “0” regardless of the size of the image data, and the least significant bit is stored in the image data. In response, “1” or “0” is set. In the next red exposure sequence, the red image data of the (M + 1) -th line and the M-th line are read out and converted into mirror drive data in the same manner. Each color image memory 31 to 33 stores one line of dummy data that does not cause the pixel PS to develop color as image data of the 0th line.

  The data write control circuit 35 responds to the Mth line in synchronization with the timing pulse from the controller 30 when the image data of the Mth line and the (M−1) th line are read from the image memory. The mirror drive data to be written is sequentially written into the memory cells corresponding to the first micromirror array 51. Similarly, the mirror drive data corresponding to the (M−1) th line is written in the memory cell corresponding to the second microarray 52.

  The operation of the above configuration will be described with reference to FIG. The red image data of the 0th line and the 1st line is read from the red image memory 31 and sent to the data conversion circuit 34. The data conversion circuit 34 converts each red image data into mirror drive data. At this time, all the bits of the mirror drive data on the 0th line are converted to “0”.

  When the first to fourth timing pulses are generated in sequence, the data write control circuit 35 sequentially starts the first micromirror from the upper 1st bit to the upper 4th bit of each mirror drive data on the first line. Write to the memory cells of array 51. As a result, each micromirror 12 of the first micromirror array 51 is driven in the same manner as in the above embodiment, and receives red light from the red LED device 20 that is continuously lit during the first to fourth subsequences. The red sub-exposure from the first to the fourth time is performed on the first line of the photographic paper 41.

  On the other hand, the mirror drive data of the upper 1st bit to the upper 4th bit of the 0th line are sequentially written into the memory cells of the second micromirror array 52, but each bit is “0”. During the first to fourth subsequences, the micromirrors 12 of the second micromirror array 52 are maintained in the invalid reflection state, and the red exposure is not performed on the portion of the photographic paper 41 before the first line. .

  Next, when the fifth timing pulse is generated, the least significant bit of “0” of each mirror drive data of the first line is written in each memory cell of the first micromirror array 51. Each micromirror 51 of the micromirror array 51 is in an invalid reflection state. Further, the least significant bit of the mirror drive data is also written in the memory cells of the second micromirror array 52. Thus, when the least significant bit is written in the memory cells of the micromirror arrays 51 and 52, the lighting control means lights the red LED device 20 for the time 1/32 · T. Since “0” is written, red exposure is not performed on the photographic paper 41 at this time.

  Thereafter, similar to the red exposure sequence, the green exposure sequence is performed based on the green image data of the 0th line and the 1st line. Further, a blue exposure sequence is performed based on the blue image data of the 0th line and the 1st line. As a result, as indicated by hatching in FIG. 9A, the first line 61 of the photographic printing paper 41 is driven by the first to fourth bits of the three colors of mirror drive data. It will be in the state exposed by.

  When the exposure for the three colors on the first line is completed, the second red exposure sequence is started after the printing paper 41 is fed for one line. The red image data of the first line and the second line are read from the red image memory 33, sent to the data conversion circuit 34, and converted into mirror drive data, respectively.

  Next, in synchronization with the first to fourth timing pulses, the data write control circuit 35 sequentially starts from the upper 1st bit to the upper 4th bit of each mirror drive data on the second line. Data is written in the memory cell of the micromirror array 51. As a result, each micromirror 12 of the first micromirror array 51 is driven and irradiated with red light from the continuously lit red LED device 20, and the second line 62 of the photographic paper 41 receives red light from the first time. The red sub-exposure up to the fourth time is performed.

  Further, the mirror drive data of the upper first bit to the upper fourth bit of the first line are sequentially written into the memory cells of the second micromirror array 52, but these are “0”. During the fourth sub-sequence, each micromirror 12 of the second micromirror array 52 is maintained in the invalid reflection state, and the first line 61 of the photographic paper 41 is not exposed to red.

  When the fifth timing pulse is generated, all the micromirrors 12 of the first micromirror array 51 are in an invalid reflection state by the least significant bit of “0” of the mirror drive data. Further, the least significant bit of each mirror drive data on the first line is written into the memory cell of the second micromirror array 52. At this time, since the least significant bit of the mirror drive data corresponding to the pixel PS to be subjected to red exposure at time 1/32 · T among the pixels PS of the first line is “1”, the red image data The micromirror 12 corresponding to the above becomes an effective reflection state.

  When a predetermined time elapses after the fifth timing pulse is generated, the lighting control circuit 29 sends a lighting control signal to turn on the red LED device 20 for a time 1/32 · T as shown in FIG. To do. As a result, the spot light reflected by the micromirror 12 which is in the effective reflection state of the second micromirror array 52 during this fifth subsequence is projected onto the first line 61, and the time 1 is projected onto this first line 61. / 32 · T red sub-exposure is performed.

  When the red exposure sequence is thus completed, the green and blue exposure sequences are sequentially performed in the same procedure. As a result, as shown in FIG. 9B, the first line 61 has sub-exposure of the previous three-color exposure sequence and sub-exposure of time 1/32 · T by the current three-color exposure sequence. And is done. Therefore, each pixel PS of the first line 61 has its three color exposure amounts adjusted in 32 stages. Further, regarding the second line 62, each of the three colors is exposed by the first bit to the fourth bit of the mirror drive data of the second line.

  Thereafter, after the photographic printing paper 41 is conveyed by one line, an exposure sequence for each color is performed in the same manner as described above based on the image data of each color of the second line and the third line. As a result, as shown in FIG. 9C, the second line 62 is exposed in 32 steps for each color, and the third line 63 is the top one of the mirror drive data of the third line for each of the three colors. The exposure is performed from the 4th bit to the 4th bit. Thereafter, the third and subsequent lines are sequentially recorded in the same manner.

  In this way, the same effect as in the above embodiment can be obtained even when two micromirror arrays 51 and 52 are used. Further, even when the response speed of the micromirror 12 is slow, each micromirror 12 of the second micromirror array 52 can be driven at an appropriate timing, so that it can be controlled without increasing the exposure sequence time. The exposure time can be further reduced. That is, when the number of gradations that can be recorded is increased, it is not necessary to slow down the recording speed even if a micromirror with a slow response speed is used. On the other hand, when a micromirror having a high response speed is used, high-speed recording can be performed without providing a large number of micromirror arrays even if the number of gradations that can be recorded is increased.

  As shown in FIG. 11, it had A group consisting of three first to third micromirror arrays A1 to A3 and B group consisting of three fourth to sixth micromirror arrays B1 to B3. Using the digital micromirror device 60, it is also possible to perform image recording at a higher speed by feeding one line of photographic paper every time one color is exposed.

  The case where the digital micromirror device 60 is used will be described below. In addition, parts other than those described below are the same as those in the above-described embodiment, and components having substantially the same functions will be described with the same reference numerals.

  During each exposure sequence, image data corresponding to the colors to be exposed for six consecutive rows is read from the image memory. For example, in the red exposure sequence, red image data from the Mth line to the (M-5) th line is read and sent to the data conversion circuit 34.

  For each red image data from the Mth line to the (M-2) th line, the data conversion circuit 34 sets “1” corresponding to the red image data from the upper 1st bit to the upper 4th bit of the mirror drive data. ”Or“ 0 ”, and the least significant bit is set to“ 0 ”regardless of the size of the red image data. For the (M-3) th line to the (M-5) th line, the upper 1st bit to the upper 4th bit of the mirror drive data are set to “0” regardless of the size of the image data, The least significant bit is set to “1” or “0” according to the image data. When the number of the line to be read is “0” or less, dummy data is read as in the above embodiment.

  The write control circuit 35 writes the mirror drive data created based on the red image data of the Mth line to the memory cells of the first micromirror array A1 of the A group, and drives the first micromirror array A1. . Similarly, the second micromirror array A2 is driven by the mirror drive data of the (M-1) th line, and the third micromirror array A3 is driven by the mirror drive data of the (M-2) th line.

  On the other hand, the mirror drive data created based on the red image data of the (M-3) th line is written into the memory cells of the fourth micromirror array B1 of the B group. As a result, the fourth micromirror array B1 is driven. Similarly, the fifth micromirror array B2 is driven by the mirror drive data of the (M-4) th line, and the sixth micromirror array B3 is driven by the mirror drive data of the (M-5) th line.

  In the first to fourth sub-sequences in the red exposure sequence, since the red LED device 20 is continuously lit, the first to third micromirror arrays A1 to A3 respectively (from the Mth line of the photographic paper 41 to ( M-2) Red sub-exposure up to 1/16 · T is performed for the line.

  Further, in the fifth sub-sequence, while the micromirror arrays B1 to B3 of the B group are in the effective reflection state or the invalid reflection state according to the least significant bit of the mirror drive data for the time 1/16 · T, Since the red LED device 20 is lit only for time 1/32 · T, the time 1 / (M-3) to the (M-5) th line is obtained by the micromirror arrays B1 to B3 of the B group. 32 · T red sub-exposure is performed.

  In this way, when the red exposure sequence is completed, the printing paper 41 is fed for one line, and then the green exposure sequence is started. In this green exposure sequence, green image data from the (M + 1) -th line to the (M-4) -th line is read, and mirror drive data is created in the same manner as described above based on these green image data. The first micromirror array A1 is driven by mirror drive data corresponding to the (M + 1) th line, and the second micromirror array A2 is driven by mirror drive data corresponding to the Mth line. Similarly, each of the micromirror arrays A3, B1 to B3 is driven by mirror drive data corresponding to green image data from the (M-1) th line to the (M-4) th line.

  When the green exposure sequence is completed, the photographic printing paper 41 is fed by one line, and thereafter the blue image data from the (M + 2) th line to the (M-3) th line is read, and these blue image data are read out. Based on the generated mirror drive data, the micromirror arrays A1 to A3 and B1 to B3 are driven. When this blue exposure sequence ends, the micromirror arrays A1 to A3 and B1 to B3 are driven based on the red image data from the (M + 3) th line to the (M-2) th line.

  FIG. 12 shows the recording states of the first line to the seventh line of the photographic paper 41 and the recording microarray codes when recording is performed in this way. Note that the exposure states indicated by “R, G, B” in FIG. 12 indicate that red, green, and blue exposures are performed on the line according to the first to fourth subsequences. . The exposure state indicated by “r, g, b” indicates that the line is subjected to 1/32 · T exposure of red, green, and blue in the fifth subsequence.

In this way, each line passes through the three micromirror arrays A1 to A3, so that the sub-exposure by the first to fourth subsequences for the three colors is performed, and the three micromirror arrays B1 to B3. Passes, sub-exposure is performed by the fifth sub-sequence for three colors. Thereby, each pixel PS of each line of the photographic paper 41 is recorded with 32 gradations of each color.
As described above, the micromirror arrays A1 to A3 in the A group are driven to adjust the exposure time in the first to fourth sub-sequences, and the micromirror arrays B1 to B3 in the B group are driven and By adjusting the lighting time of the light source, the exposure time of 1/32 · T is controlled, so that it is three times as long as the exposure of three colors is performed every time one line of the photographic paper 41 is sent. High-speed recording can be performed. On the other hand, even when a digital micromirror device with a response speed of 1/3 is used, a speed equivalent to that in which exposure of three colors is performed every time one line of printing paper 41 is sent can be obtained.

  In the embodiment described above, the number of micromirror arrays in each of the A group and the B group is three, but may be three or more. When the number of micromirror arrays in each group is three or more, the number of micromirror arrays in each group is set to a multiple of three so that the number of sequences of each color executed on each line is the same. Good. For example, if the number of micromirror arrays in each group is nine, recording can be performed three times faster than three. Moreover, the number of A group and B group may differ.

  In each of the above embodiments, the exposure time of 1/32 · T is adjusted by adjusting the lighting time of the light source during the fifth subsequence of time 1/16 · T, but the same subsequence is further executed. Then, the lighting time of the light source is adjusted during each sub-sequence to perform exposure of 1/32 · T, 1/64 · T, 1/64 · T, 1/128 · T,. it can. Also, if the minimum exposure time limited by the response time of the micromirror is even shorter, the exposure time of the micromirror is set to an effective reflection state, which is a smaller exposure time, for example, exposure up to time 1/32 · T. You may perform exposure of 1/64 * T by lighting time. In each of the above-described embodiments, the exposure is performed in order from the sub-sequence with the long exposure time.

  Further, in each of the above embodiments, during the fifth sub-sequence, the lighting time of the light source is modulated to 1/32 · T to perform the exposure for this time, but the light emission luminance of the LED device is modulated. Thus, an exposure amount corresponding to the exposure time 1/32 · T may be given to the photosensitive material. For example, if the light emission luminance of the LED device is ½ of the other sub-sequence and the lighting time is 1/16 · T during the fifth sub-sequence, an exposure amount corresponding to the exposure time 1/32 · T is obtained. be able to. The light emission luminance of the LED device can be adjusted by changing the duty ratio of the drive pulse supplied to the LED device.

  In each of the above embodiments, the photographic paper is intermittently fed, but may be continuously fed. The present invention can also be used in a printer including a piezo-type micromirror device. Furthermore, the present invention can also be used for a printer including an area type micromirror device in which a plurality of micromirrors are arranged in a matrix.

The silver halide color photographic light-sensitive material used in the present invention is described in detail below.
First, the metal complex represented by the following general formula (D1) used in the present invention will be described. In addition, the metal complex represented by the general formula (D1) is a complex (high contrast complex) used to make the gradation of the photosensitive material high.

General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different. However, the metal complex represented by the general formula (D1) does not have or has one CN ion as a ligand.

  Among the metal complexes represented by the general formula (D1), a metal complex represented by the following general formula (D1A) is preferable.

General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
In the general formula (D1A), M ^D1A represents Re, Ru, Os, or Rh, and X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, and represents H ₂ O, OH or O when M ^D1A is Rh. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different. X ^D1A has the same meaning as X ^{D1 in} formula (D1), and the preferred range is also the same.

  Although the preferable specific example of a metal complex represented by general formula (D1) below is given, this invention is not limited to these.

[ReCl ₆ ] ^2-
[ReCl ₅ (NO)] ^2-
[RuCl ₆ ] ^2-
[RuCl ₆ ] ^3-
[RuCl ₅ (NO)] ^2-
[RuCl ₅ (NS)] ^2-
[RuBr ₅ (NS)] ^2-
[OsCl ₆ ] ^4-
[OsCl ₅ (NO)] ^2-
[OsBr ₅ (NS)] ^2-
[RhCl ₆ ] ^3-
[RhCl ₅ (H ₂ O)] ^2-
[RhCl ₄ (H ₂ O) ₂ ] ^-
[RhBr ₆ ] ^3-
[RhBr ₅ (H ₂ O)] ^2-
[RhBr ₄ (H ₂ O) ₂ ] ^-
[PdCl ₆ ] ^2-
[PtCl ₆ ] ^2-
Among these, [OsCl ₅ (NO)] ²⁻ or [RhBr ₆ ] ³⁻ is particularly preferable.
The metal complex represented by the following general formula (D2) used in the present invention will be described.
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
In General Formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2 represents an arbitrary ligand different from X ^D2 . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2 may be the same or different from each other, and when a plurality of L ^D2 are present, these may be the same or different.

In the above, the pseudohalogen (halogenoid) ion is an ion having properties similar to a halogen ion. For example, a cyanide ion (CN ⁻ ), a thiocyanate ion (SCN ⁻ ), a selenocyanate ion (SeCN ^−). ), Tellurocyanate ion (TeCN ⁻ ), azidodithiocarbonate ion (SCSN ₃ ⁻ ), cyanate ion (OCN ⁻ ), thunderate ion (ONC ⁻ ), azide ion (N ₃ ⁻ ) and the like.

X ^D2 is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride Particularly preferred are ions and bromide ions. L ^D2 is not particularly limited and may be an inorganic compound or an organic compound, and may be charged or uncharged, but may be an uncharged inorganic compound or organic compound. preferable.

  Among the metal complexes represented by the general formula (D2), a metal complex represented by the following general formula (D2A) is preferable.

General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding cyanate ion), and L ^D2A represents an arbitrary inorganic ligand different from X ^D2A . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2A may be the same or different from each other, and when a plurality of L ^D2A are present, these may be the same or different.

X ^D2A has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2A is preferably water, OCN, ammonia, phosphine, or carbonyl, and particularly preferably water.

  Among the metal complexes represented by the general formula (D2), the metal complex represented by the following general formula (D2B) is more preferable.

General formula (D2B)
^{_{[IrX D2B n L D2B (6}} -n)] m
In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or a base structure thereof Represents a ligand in which some carbon or hydrogen atoms are replaced by other atoms or atomic groups. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Bs may be the same as or different from each other, and when there are a plurality of L ^D2Bs , these may be the same or different.

X ^D2B has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2B represents a ligand in which a chain or cyclic hydrocarbon is a base structure, or a carbon or hydrogen atom in a part of the base structure is replaced with another atom or atomic group, but cyanide Ions are not included. L ^D2B is preferably a heterocyclic compound. More preferably, it is a 5-membered ring compound, and among the 5-membered ring compounds, a compound containing at least one nitrogen atom and at least one sulfur atom in the 5-membered ring skeleton is more preferable.

  Among the metal complexes represented by the general formula (D2B), a metal complex represented by the following general formula (D2C) is more preferable.

General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (except a cyanate ion). L ^D2C is a 5-membered ring ligand which represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. It's okay. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2Cs may be the same as or different from each other, and when a plurality of L ^D2Cs are present, these may be the same or different.

X ^D2C has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. The substituent on the carbon atom in the ring skeleton in L ^D2C is preferably a substituent having a smaller volume than the n-propyl group. As substituents, methyl group, ethyl group, methoxy group, ethoxy group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, formyl group, thioformyl group, hydroxy group, mercapto group, amino group, hydrazino group , An azido group, a nitro group, a nitroso group, a hydroxyamino group, a carboxyl group, a carbamoyl group, and a halogen atom (fluoro group, chloro group, bromo group, iodo group) are preferred.

  Although the preferable specific example of a metal complex represented by general formula (D2) below is given, this invention is not limited to these.

[IrCl ₅ (H ₂ O)] ^2-
[IrCl ₄ (H ₂ O) ₂ ] ^-
[IrCl ₅ (H ₂ O)] ^-
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ^3-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (OH)] ^2-
[IrCl ₄ (OH) ₂ ] ^-
[IrCl ₅ (O)] ^4-
[IrCl ₄ (O) ₂ ] ^5-
[IrCl ₅ (O)] ^3-
[IrCl ₄ (O) ₂ ] ^4-
[IrBr ₅ (H ₂ O)] ^2-
[IrBr ₄ (H ₂ O) ₂ ] ^-
[IrBr ₅ (H ₂ O)] ^-
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ^3-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (OH)] ^2-
[IrBr ₄ (OH) ₂ ] ^-
[IrBr ₅ (O)] ^4-
[IrBr ₄ (O) ₂ ] ^5-
[IrBr ₅ (O)] ^3-
[IrBr ₄ (O) ₂ ] ^4-
[IrCl ₅ (OCN)] ^3-
[IrBr ₅ (OCN)] ^3-
[IrCl ₅ (thiazole)] ^2-
[IrCl ₄ (thiazole) ₂ ] ^-
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ^2-
[IrBr ₄ (thiazole) ₂ ] ^-
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ^2-
[IrCl ₄ (5-methylthiazole) ₂ ] ^-
[IrBr ₅ (5-methylthiazole)] ^2-
[IrBr ₄ (5-methylthiazole) ₂ ] ^-
Among these, [IrCl ₅ (5-methylthiazole)] ^2- is particularly preferable.

  The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do.

Metal complex represented by the general formula (D1), preferably added 1 × 10 ^-6 mol 1 × 10 ^-11 mol per mol of silver in the grain formation, 1 × 10 from 1 × 10 ^-10 mol ^-6 mol is more preferable, and 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁷ mol is most preferable. Metal complex represented by the general formula (D2), preferably added 1 × 10 ^-3 mol 1 × 10 ^-10 mol per mol of silver in the grain formation, 1 × 10 from 1 × 10 ^-8 mol It is most preferable to add ^-5 mol.

  In the present invention, the above metal complex is preferably added with a solution dissolved and kept warm at pH 4.0 to 10.0 and 0 to 25 ° C. in order to prevent changes in valence and ligand.

  In the present invention, the above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or in other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the metal complex has been previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing the complex only inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but a hexacoordinate complex having Ir as a central metal, in which all six ligands are Cl, Br, or I, has a silver bromide concentration maximum. It is preferable to contain.

Next, the photographic layers of the silver halide color photographic light-sensitive material for movie projection of the present invention will be described.
The silver halide color photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material having a transmissive support, and a plurality of silver halides each having red sensitivity, green sensitivity and blue sensitivity on the support. A silver halide color photographic light-sensitive material having a light-sensitive layer composed of an emulsion layer. The present invention can be applied to color photographic light-sensitive materials for general use such as color positive film and movie positive film and movie. In particular, it is preferably applied to a color positive photosensitive material for movies.

  In the present invention, the number and order of the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer are not particularly limited. Each of the yellow, cyan and magenta color-sensitive photosensitive silver halide emulsion layers is composed of a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities, even if the photosensitive silver halide emulsion layer is composed of one photosensitive silver halide emulsion layer. It may be.

  There is no restriction between the color developability and color sensitivity of each color-sensitive photosensitive silver halide emulsion layer. For example, a color developable light-sensitive silver halide emulsion layer has color sensitivity in the infrared region. It doesn't matter.

  Examples of typical layer order include a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye and / or black colloidal silver in order from the support, a yellow color-forming photosensitive silver halide emulsion layer, a non-photosensitive layer. Hydrophilic colloid layer (color mixing prevention layer), cyan color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing preventing layer), magenta color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic Colloidal layer (protective layer). However, depending on the purpose, the order of installation may be changed, or the number of photosensitive silver halide emulsion layers or non-photosensitive hydrophilic colloid layers may be increased or decreased.

The iron content (Fe) in the silver halide color photographic light-sensitive material of the present invention is mainly introduced by gelatin, intentionally doped emulsion grains, dyes, etc., but the Fe content in the light-sensitive material of the present invention is as follows. The Fe content must be 2 × 10 ⁻⁵ mol / m ² or less (preferably 1 × 10 ⁻⁸ to 2 × 10 ⁻⁵ mol / m ² ), and 8 × 10 ⁻⁶ mol / m 2. ² or less (preferably 1 × 10 ⁻⁸ to 8 × 10 ⁻⁶ mol / m ² ) is preferable, and 3 × 10 ⁻⁶ mol / m ² or less (preferably 1 × 10 ^{−8 to} 3 × 10 ⁻⁶ mol / m ² ). m ² ) is most preferred.

  In the present invention, gelatin is preferably used as the hydrophilic colloid. If necessary, other hydrophilic colloids can be used in place of gelatin at any ratio. Examples of these include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin or casein, cellulose derivatives (eg, hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate), saccharides such as sodium alginate and starch derivatives. And a wide range of synthetic polymers such as polyvinyl alcohol, partial acetal of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole.

  Examples of the silver halide grains used in the present invention include silver chloride, silver bromide, (iodo) silver chlorobromide, and silver iodobromide. In particular, in the present invention, silver chloride, silver chlorobromide, silver chloroiodide and silver chloroiodobromide having a silver chloride content of 95 mol% or more can be preferably used in order to speed up the development processing time. The silver halide grains in this emulsion are those having regular crystals such as cubes, octahedrons and tetradecahedrons, those having irregular crystal systems such as spheres and plates, twin planes, etc. Those having the above crystal defects or a composite system thereof may be used. Further, it is preferable to use tabular grains whose main plane is the (111) plane or the (100) plane in terms of speeding up color development and reducing processing color mixing. Regarding tabular high silver chloride emulsion grains having a principal plane of (111) plane or (100) plane, JP-A-6-138619, U.S. Pat. Nos. 4,399,215, 5,061,617, 5,320,938, 5,264,337, 5,292,632, 5,314,798, 5,413,904, International Publication WO94 / 22051 It can be prepared by the method disclosed in each gazette or specification of the issue.

  As the silver halide emulsion that can be used together in the present invention, a silver halide emulsion having an arbitrary halogen composition may be used. From the viewpoint of rapid processability, a salt (iodinated) salt having a silver chloride content of 95 mol% or more. Silver and silver (iodo) bromide are preferred, and silver halide emulsions having a silver chloride content of 95 mol% or more are preferred as in the emulsion used in the present invention.

  The sphere equivalent diameter of the silver halide grains constituting the silver halide emulsion used in the present invention is preferably 0.25 μm or less, more preferably 0.20 μm or less, and 0.18 μm or less. The lower limit is not particularly limited, but is usually 0.05 μm, preferably 0.10 μm or more. In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. Particles with a sphere equivalent diameter of 0.25 μm correspond to cubic particles with a side length of about 0.20 μm, particles with a sphere equivalent diameter of 0.20 μm correspond to cubic particles with a side length of about 0.16 μm, and a sphere equivalent diameter of 0.18 μm. These particles correspond to cubic particles having a side length of about 0.14 μm.

  The emulsion used in the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation coefficient of the sphere equivalent diameter of all particles used in the present invention is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter.

  The silver halide emulsion used in the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used. The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced. For gold sensitization, a compound such as chloroauric acid or a salt thereof, gold thiocyanate or gold thiosulfate can be used. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. Is more preferable.

  Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation and types”, and 18716 (November 1979), page 648, ibid. 307105 (November 1989), 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Monter (P. Glafkides, Chemie et Physiograph Photograph, Paul Montel, 1967), "Photoemulsion Chemistry". Published by Focal Press (GF Duffin, Photographic Chemistry Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions" by Zelikman et al., Published by Focal Press (V. L. Zelikman, et al.,). (Making and Coating Photographic Emulsion, Focal Press, 1964) and the like. .

  Monodispersed emulsions described in US Pat. Nos. 3,574,628, 3,655,394, and British Patent 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); U.S. Pat. No. 4,434,226, 4 No. 4,414,310, No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. Also, a mixture of various crystal grains may be used.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. . Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

  As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. The additive used in such a process is RDNo. 17643, ibid. 18716 and the same No. 307105, and the corresponding sections are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The coating amount of silver in film for a silver halide color photographic light-sensitive material of the present invention is preferably 6.0 g / m ² or less, more preferably 4.5 g / m ² or less, 2.0 g / m ² or less and most preferably . The applied silver amount is 0.01 g / m ² or more, preferably 0.02 g / m ² or more, more preferably 0.5 g / m ² or more.

In any one of the photographic constituent layers composed of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer (intermediate layer, protective layer, etc.) provided on the support, preferably a silver halide emulsion layer The 1-aryl-5-mercaptotetrazole compound is preferably added in an amount of 1.0 × 10 ^{−5 to} 5.0 × 10 ⁻² mol, and more preferably 1.0 × 10 ⁻⁴ to 1 per mol of silver halide. It is preferable to add 0.0 × 10 ⁻² mol. By adding in this range, the stain on the processed color photographic surface after the continuous processing can be further reduced.

As such a 1-aryl-5-mercaptotetrazole compound, an aryl group at the 1-position is preferably an unsubstituted or substituted phenyl group, and preferred specific examples of this substituent include acylamino groups (for example, acetylamino, -NHCOC ₅ H ₁₁ (n) etc.), ureido group (eg methylureido etc.), alkoxy group (eg methoxy etc.), carboxylic acid group, amino group, sulfamoyl group etc. A plurality (2 to 3 etc.) may be bonded. Further, the position of the substituent is preferably the meta or para position. Specific examples thereof include 1- (m-methylureidophenyl) -5-mercaptotetrazole and 1- (m-acetylaminophenyl) -5-mercaptotetrazole.

  The photographic additive that can be used or used in the present invention is described in the following Research Disclosure Journal (RD), and the following description is given.

Various dye-forming couplers can be used in the silver halide color photographic light-sensitive material of the present invention, and the following dye-forming couplers are particularly preferred.

  Yellow coupler: coupler represented by general formulas (I) and (II) of European Patent EP502,424A; coupler represented by general formulas (1) and (2) of European Patent EP513,496A (Especially Y-28 on page 18); couplers represented by general formula (I) of claim 1 of JP-A-5-307248; 45-1 of column 1 of US Pat. No. 5,066,576 Coupler represented by general formula (I) on line 55; coupler represented by general formula (I) in paragraph 0008 of JP-A-4-274425; claim 40 on page 40 of EP 498,381A1 (Especially D-35 on page 18); couplers represented by general formula (Y) on page 4 of European Patent EP447,969A1 (especially Y-1 (page 17), Y-54 ( 41)); United States The couplers represented by the formulas (II) to (IV) in columns 7 to 58 of column 7 of the specification No. 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19) )).

  Magenta coupler: JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13)); European Patent EP 456,257 A-4-63 (page 134), A-4-73, -75 (page 139); European Patent EP 486,965, M-4, -6 (page 26), M-7 (page 27). ); M-45 in paragraph 0024 of JP-A-6-43611, M-1 in paragraph 0036 in JP-A-5-204106; M-22 in paragraph 0237 of JP-A-4-362631.

  Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14 to 16) of JP-A-4-204843; C-7,10 (35 of JP-A-4-43345) Pages), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); and general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385 Coupler represented by Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.

  Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, German Patent GB 2,125570, European Patent EP 96,873B, German Patent DE 3,234,533. Those described in the document are preferred. A coupler for correcting unwanted absorption of the coloring dye is yellow represented by the general formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1. Colored Cyan Coupler (especially YC-86 on page 84), Yellow Colored Magenta Coupler ExM-7 (page 202, EX-1 (page 249), EX-7 (page 251), US Patent) described in the European Patent Specification No. 4,833,069, magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10), US 4,837,136 (2) (column 8), International Publication WO92 / A colorless masking coupler represented by the general formula [C-1] of claim 1 of No. 11575 (particularly, exemplified compounds on pages 36 to 45) is preferable.

Examples of compounds (including dye-forming couplers) that react with oxidized developing agents to release photographically useful compound residues include the following.
Development inhibitor releasing compound: a compound represented by any one of the general formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (particularly T-101) (Page 30), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), European Patent EP 436, The compound represented by the general formula (I) described on page 7 of the specification of 938A2 (particularly D-49 (page 51)), the compound represented by the general formula (1) of JP-A-5-307248 ( In particular, the compound represented by any one of the general formulas (I), (II) and (III) described in paragraph (0027) (23)) and pages 5 to 6 of European Patent EP440,195A2 (particularly page 29) I- (1));
Bleach accelerator releasing compounds: compounds represented by general formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (61) on page 61) and JP-A-6 Compound represented by the general formula (I) of claim 1 of JP-A-59411 (particularly, paragraph (7) of paragraph 0022); ligand releasing compound: described in claim 1 of US Pat. No. 4,555,478 A compound represented by LIG-X (particularly, a compound on the 21st to 41st lines of column 12);
Leuco dye releasing compounds; compounds 1-6 of columns 3-8 of US Pat. No. 4,749,641;
Fluorescent dye-releasing compound: a compound represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (particularly compounds 1 to 11 in columns 7 to 10);
Development accelerator or fogging agent releasing compound: compound represented by general formula (1), (2), (3) in column 3 of U.S. Pat. No. 4,656,123 (especially (I- 22)) and ExZK-2 on page 75, lines 36-38 of EP 450,637A2; a compound which releases a group which becomes a dye only after leaving: Claim 1 of US Pat. No. 4,857,447 A compound represented by the general formula (I): (especially Y-1 to Y-19 in columns 25 to 36).

  As additives other than the dye-forming coupler, the following are preferable.

Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140) of JP-A-62-215272 ˜144);
Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363;
Oxidizing agent scavenger for developing agent: Compound (especially I- (1), (2), (6) in column 2, lines 54 to 62 of U.S. Pat. No. 4,978,606. ), (12) (columns 4-5)), U.S. Pat. No. 4,923,787, column 2, line 5-10, in particular compound 1 (column 3);
Stain inhibitor: General formulas (I) to (III) on page 4, lines 30 to 33 of EP 298321A, in particular I-47, 72, III-1, 27 (pages 24 to 48);
Antifading agent: A-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (69 of EP 298321A) -118), U.S. Pat.No. 5,122,444, columns 25-38, II-1 to III-23, especially III-10, and EP 471347A, pages 8-12, I-1. ~ III-4, in particular II-2, U.S. Pat. No. 5,139,931, columns 32-40, A-1 to 48, in particular A-39,42;
Materials that reduce the amount of color-enhancing agent or color mixing inhibitor used: I-1 to II-15, especially I-46, pages 5 to 24 of EP 4131324A;
Formalin scavenger: European patent EP 477932A, pages 24 to 29, SCV-1 to 28, in particular SCV-8;
Hardener: H-1,4,6,8,14 on page 17 of JP-A-1-214845, general formula (VII) to columns 13-23 of U.S. Pat. No. 4,618,573 Compound (H-1 to 54) represented by (XII), Compound (H-1 to 76) represented by formula (6) at the lower right of page 8 of JP-A-2-214852, particularly H-14 A compound according to claim 1 of US Pat. No. 3,325,287;
Development inhibitor precursor: compounds described in claim 1 of P-24, 37, 39 (pages 6-7) of JP-A No. 62-168139, US Pat. No. 5,019,492, particularly column 7 28-29;
Preservatives, antifungal agents: U.S. Pat. No. 4,923,790, columns 3-15, I-1 to III-43, in particular II-1,9,10,18, III-25;
Stabilizer, antifoggant: US Pat. No. 4,923,793, columns 6-16, I-1 to (14), in particular I-1,60, (2), (13), US Pat. Compounds 1 to 65, in particular 36, in columns 25 to 32 of 4,952,483;
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324;
Dye: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially a-1, 12, 18, 27, 35, 36, b-5, pages V to 27 to 29 -23, in particular V-1, F-I-1 to F-II-43, in particular F-I-11, F-II-8, European patent EP 457153A, on pages 33 to 55 of EP 445627A. Pp. 17-28, III-1 to 36, especially III-1,3, European Patent EP 319999A, pages 6 to 11, Compounds 1 to 22, especially Compound 1, European Patent EP 519306A Compounds D-1 to 87 represented by (1) to (3) (pages 3 to 28), Compounds 1 to 22 represented by general formula (I) in U.S. Pat. No. 4,268,622 Columns 3-10), U.S. Pat. No. 4,923,788. A compound represented by the general formula (I) (1) ~ (31) (columns 2-9);
UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by general formula (1) in JP-A No. 46-3335, and general formulas of European Patent EP520938A Compounds (3) to (66) (pages 10 to 44) represented by (I) and compounds HBT-1 to HBT-10 (page 14) represented by general formula (III), European Patent EP521823 Compounds (1) to (31) represented by general formula (1): (columns 2 to 9).

  In the present invention, non-bleachable colored materials are preferably used in combination. The non-bleachable colored material does not come out of bath or lose color during development processing, and the light absorption characteristics in the film before and after the processing are practically unchanged. There is no restriction | limiting in particular about the kind, Various dyes and pigments containing a well-known substance can be used.

  Known dyes include, for example, oxonol dyes, azomethine dyes, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, arylidene dyes, styryl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, azine dyes, oxazines And dyes, thiazine dyes, perinone dyes, merocyanine dyes, cyanine dyes, indoaniline dyes, phthalocyanine dyes, indigo dyes, and thioindigo dyes.

  As for known pigments, for example, azo pigments (insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments), phthalocyanine pigments, dyed lake pigments (acidic dye lakes, basic dye lakes), condensation Organics such as polycyclic pigments (quinacridone pigments, thioindigo pigments, perylene pigments, anthraquinone pigments, perinone pigments, dioxazine pigments, isoindolinone pigments, diketopyrrolopyrrole pigments) and others (nitroso pigments, alizarin lake pigments, alkali blue) Mention may be made of pigments.

  For specific compounds, please refer to “New Edition Dye Handbook” (Organic Synthetic Chemistry Association; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Color Material Engineering Handbook” (Color Material Association Edition; Asakura Shoten) 1989), “Revised New Handbook of Pigments” and the like. As specific examples of preferred dyes and pigments, D-1 to D-35 and P-1 to P-30 described in paragraph No. 0191 to paragraph No. 0250 of JP-A No. 11-95371 can be preferably exemplified. In addition, the method for adding these to the light-sensitive material is also described in detail in paragraph Nos. 0206 to 0215 of the patent, and these described parts are incorporated as part of the specification of the present application.

In the present invention, among the above, preferably better dye than the pigment, although the amount used 1 to 100 mg / m ² is generally preferably 5 to 100 mg / m ^2, more preferably 10 to 50 mg / m ² .

  The silver halide color photographic light-sensitive material of the present invention preferably contains a compound represented by the following general formula (FS) as a surfactant.

  In general formula (FS), A and B each independently represent a fluorine atom or a hydrogen atom. a and b each independently represent an integer of 1 to 6; c and d each independently represents an integer of 4 to 8. x represents 0 or 1; M represents a cation.

  A and B each independently represent a fluorine atom or a hydrogen atom, and A and B may be the same or different. A and B are each preferably a fluorine atom or a hydrogen atom, and more preferably both A and B are a fluorine atom.

  a and b each independently represent an integer of 1 to 6; As long as a and b are integers of 1 to 6, they may be different from each other or the same. a and b are preferably integers of 1 to 6, and a = b, more preferably an integer of 2 or 3, and a = b, and more preferably a = b = 2.

  c and d each independently represents an integer of 4 to 8. As long as c and d are integers of 4 to 8, they may be different or the same. c and d are preferably integers of 4 to 6 and c = d, more preferably 4 or 6 and c = d, and further preferably c = d = 4. .

x represents 0 or 1, both of which are likewise preferred.
M represents a cation, and as the cation represented by M, for example, alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions and the like are preferable. Applied. Of these, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

  Among the compounds represented by the general formula (FS), a compound represented by the following general formula (FS-a) is more preferable.

  In general formula (FS-a), a, b, c, d, M, and x have the same meanings as those in general formula (FS), and preferred ranges thereof are also the same.

  Among the general formula (FS), the following general formula (FS-b) is more preferable.

  In general formula (FS-b), a1 represents the integer of 2-3. c1 represents an integer of 4 to 6. M represents a cation. x represents 0 or 1;

  2 is preferable as a1. c1 is preferably 4. x is preferably 0 or 1.

  Although the specific example of the preferable surfactant used for this invention is illustrated below, this invention is not limited to these specific examples.

  In the present invention, when the surfactant is used in the layer of the photographic material, the aqueous coating composition containing the surfactant may be composed of only the surfactant used in the present invention and water, depending on the purpose. And may contain other components as appropriate.

  In the above aqueous coating composition, two kinds of surfactants used in the present invention may be used according to the combination defined in the present invention, or three or more kinds may be mixed and used. Moreover, you may use another surfactant within the structure prescribed | regulated to this invention with the surfactant used for this invention. Examples of the surfactant that can be used in combination include various anionic, cationic, and nonionic surfactants, and may be a polymeric surfactant. Of these, anionic or nonionic active agents are more preferred. Examples of surfactants that can be used in combination include, for example, JP-A-62-215272 (pages 649 to 706), Research Disclosure (RD) Item 17643, pages 26 to 27 (December 1978), 18716,650. Page (November 1979), 307105, pages 875-876 (November 1989), and the like.

  A representative compound that may be contained in the aqueous coating composition is a polymer compound. The polymer compound may be a polymer soluble in an aqueous medium or an aqueous dispersion of a polymer (so-called polymer latex). The soluble polymer is not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the polymer latex includes various vinyl monomers (for example, acrylates). Derivatives, methacrylate derivatives, acrylamide derivatives, methacrylamide derivatives, styrene derivatives, conjugated diene derivatives, N-vinyl compounds, O-vinyl compounds, vinyl nitriles, other vinyl compounds (for example, ethylene, vinylidene chloride)) homopolymers or copolymers And a dispersion of a condensation polymer (for example, polyester, polyurethane, polycarbonate, polyamide). Detailed examples of this type of polymer compound are disclosed in, for example, JP-A-62-215272 (pages 707 to 763), Research Disclosure (RD) Item 17643, 651 (December 1978), page 18716, 650 ( 1979), 307105, 873-874 (November 1989), and the like.

  The medium in the aqueous coating composition may be water alone, or an organic solvent other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, etc.) and water. A mixed solvent may be used. The ratio of water in the aqueous coating medium is preferably 50% by mass or more.

  The aqueous coating composition may contain various compounds depending on the layer of the photographic photosensitive material to be used, and they may be dissolved in a medium or dispersed. Examples thereof include various couplers, ultraviolet absorbers, color mixing inhibitors, antistatic agents, scavengers, antifoggants, hardeners, dyes, and antifungal agents. In order to obtain effective antistatic ability and coating uniformity when used in a photographic light-sensitive material, it is preferably used for the uppermost hydrophilic colloid layer.

  In this case, in the coating composition of the layer, in addition to the hydrophilic colloid (for example, gelatin) and the fluorosurfactant used in the present invention, other surfactants, matting agents, slip agents, colloidal silica, gelatin A plasticizer or the like can be contained.

  There is no particular restriction on the amount of the surfactant represented by the general formula (FS), (FS-a) or (FS-b), and it is included in the structure of the surfactant, its use, and the aqueous composition. The amount used can be arbitrarily changed depending on the kind and amount of the compound to be prepared, the composition of the medium, and the like. For example, when the surfactant used in the present invention is used as a coating liquid for the uppermost hydrophilic colloid (gelatin) layer of a photographic photosensitive material which is a preferred embodiment of the present invention, the concentration (% by mass) in the coating solution is 0.003 to 2.0%, and preferably 0.03 to 10% based on the gelatin solid content.

In the silver halide color photographic light-sensitive material of the present invention, the total hydrophilic colloid layer on the side having the emulsion layer preferably has a total film thickness of 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, 16 μm or less is particularly preferable. The total film thickness is 0.1 μm or more, preferably 1 μm or more, and more preferably 5 μm or more. Further, the film swelling speed T _1/2 is preferably 60 seconds or less, and more preferably 30 seconds or less. T _1/2 is defined as the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed for 3 minutes at 35 ° C. with a color developer is defined as the saturated film thickness. To do. The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A. Green et al. (Photogr. ScI. Eng), Vol. 19, 2, pp. 124-129 can be used for measurement. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.

  Further, the swelling rate is preferably 180 to 280%, and more preferably 200 to 250%. Here, the swelling ratio is a scale representing an equilibrium swelling amount when the silver halide photographic light-sensitive material of the present invention is immersed in distilled water at 27 ° C. and swollen, and the swelling ratio (unit:%) = when swollen Total film thickness / total film thickness during drying × 100. The swelling ratio can be adjusted to the above range by adjusting the amount of gelatin hardener added.

  The silver halide color photographic light-sensitive material for movies of the present invention can be processed by the standard processing steps for film positive light-sensitive materials.

Standard processing (excluding drying) for conventional film positive photosensitive materials
(1) Color developing bath (2) Stop bath (3) Washing bath (4) First fixing bath (5) Washing bath (6) Bleaching acceleration bath (7) Bleaching bath (8) Washing bath (9) Sound development (Paint development)
(10) Washing with water (11) Second fixing bath (12) Washing bath (13) Stabilizing bath In the present invention, the color development time (step (1) above) is 2 minutes 30 seconds or less among the above processing steps. (The lower limit is preferably 6 seconds or more, more preferably 10 seconds or more, still more preferably 20 seconds or more, most preferably 30 seconds or more), more preferably 2 minutes or less (the lower limit is the same as 2 minutes 30 seconds) Also gives favorable results.

Hereinafter, the support will be described.
In the present invention, a transparent support is preferable, and a plastic film support is more preferable. Examples of the plastic film support include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, polystyrene, and polyethylene.

  Among these, a polyethylene terephthalate film is preferable, and a biaxially stretched and heat-set polyethylene terephthalate film is particularly preferable from the viewpoint of stability and toughness.

  Although there is no restriction | limiting in particular as thickness of the said support body, 15-500 micrometers is common, especially 40-200 micrometers is preferable from points, such as a handleability and versatility, and 85-150 micrometers is the most preferable. The transmissive support preferably means a substrate that transmits 90% or more of visible light, and contains dyed silicon, alumina sol, chromium salt, zirconium salt, etc. as long as it does not substantially interfere with light transmission. It may be.

  In order to firmly adhere the photosensitive layer to the surface of the plastic film support, the following surface treatment is generally performed. The same surface treatment is generally performed on the surface on which the antistatic layer (back layer) is formed. (1) Directly after surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxygen treatment, etc. There are two methods: a method in which a photographic emulsion (photosensitive layer forming coating solution) is applied to obtain an adhesive force, and a method (2) in which a surface layer is once treated and a subbing layer is provided and a photographic emulsion layer is applied thereon. There is a law.

  Of these, the method (2) is more effective and widely used. In any of these surface treatments, a slightly polar group is formed on the surface of the support that was originally hydrophobic, a thin layer that is a negative factor for surface adhesion is removed, It seems to increase the crosslink density and increase the adhesive strength. As a result, the affinity with the polar group of the component contained in the undercoat layer solution increases and the fastness of the adhesive surface increases. It is considered that the adhesion between the undercoat layer and the support surface is improved.

  A non-photosensitive layer containing conductive metal oxide particles is preferably provided on the surface of the plastic film support on which the photosensitive layer is not provided. As the binder for the non-photosensitive layer, acrylic resin, vinyl resin, polyurethane resin and polyester resin are preferably used. This non-photosensitive layer is preferably hardened, and as the hardener, aziridines, triazines, vinyl sulfones, aldehydes, cyanoacrylates, peptides, epoxies, melamines, etc. are used. However, from the viewpoint of firmly fixing the conductive metal oxide particles, melamine compounds are particularly preferable.

The material of the conductive metal oxide particles includes ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ and V ₂ O _5, and complex oxides thereof, and these Examples of the metal oxide further include metal oxides containing different atoms.

As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , MgO, and V ₂ O ₅ are preferable, and SnO ₂ , ZnO, In ₂ O ₃ , TiO _2, and V ₂ are further preferable. O ₅ is preferred, and SnO ₂ and V ₂ O ₅ are particularly preferred. Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₂ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. If the amount of the different element added is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. If it exceeds 30 mol%, the degree of blackening of the particles increases, and charging Since the prevention layer is darkened, it is not suitable for a photosensitive material. Accordingly, the material of the conductive metal oxide particles is preferably a material containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

  The conductive metal oxide particles are usually required to have a volume ratio of 50% or less with respect to the entire non-photosensitive layer, but preferably 3 to 30%. The coating amount is preferably in accordance with the conditions described in JP-A-10-62905. When the volume ratio exceeds 50%, dirt is likely to adhere to the surface of the processed color photograph. When the volume ratio is less than 3%, the antistatic ability does not function sufficiently.

  The particle diameter of the conductive metal oxide particles is preferably as small as possible in order to reduce light scattering as much as possible, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter, and Mie's theory Can be obtained using In general, the average particle size is 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm. Here, the average particle size is a value including not only the primary particle size of the conductive metal oxide particles but also the particle size of the higher order structure.

  When the metal oxide fine particles are added to the coating solution for forming the antistatic layer, they may be added and dispersed as they are, but they are dispersed in a solvent such as water (including a dispersant and a binder as necessary). It is preferably added in the form of a dispersion.

  The non-photosensitive layer preferably contains a cured product of the binder and the hardener as a binder for dispersing and supporting the conductive metal oxide particles. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use water-soluble binders and hardeners, or use them in an aqueous dispersion state such as an emulsion. Moreover, it is preferable that a binder has any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with a hardening agent is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of the hydroxyl group or carboxyl group in the binder is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

  Hereinafter, the resin preferably used as the binder will be described. As acrylic resin, acrylic acid; acrylic acid esters such as alkyl acrylate; acrylamide; acrylonitrile; methacrylic acid; methacrylic acid esters such as alkyl methacrylate; homopolymer of any monomer of methacrylamide and methacrylonitrile Or a copolymer obtained by polymerization of two or more of these monomers. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers Is preferred. For example, a homopolymer of any one of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or a copolymer obtained by polymerization of two or more of these monomers. .

  The acrylic resin is mainly composed of a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with the hardener is possible with the above composition as a main component. It is preferable that the polymer is obtained in the above manner.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / A (meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic ester copolymer). preferable.

  The vinyl resin is polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl holmaral, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate so that a crosslinking reaction with a hardener is possible. The other polymer is a polymer obtained by partially using a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with the hardener.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the polyester resin, for example, after the reaction between the polyol and the polybasic acid is completed, the hydroxyl group and carboxyl group remaining unreacted can be used as functional groups capable of crosslinking reaction with the hardener. Of course, a third component having a functional group such as a hydroxyl group may be added. Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

  The melamine compound preferably used as a hardener includes a compound containing two or more (preferably three or more) methylol groups and / or alkoxymethyl groups in the melamine molecule and a melamine resin which is a condensation polymer thereof. Examples include melamine and urea resin. Examples of the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, and the like. (Sumitex Resin) M-3, MW, MK, and MC (manufactured by Sumitomo Chemical Co., Ltd., all trade names), but are not limited thereto.

  Examples of the condensation polymer include hexamethylol melamine resin, trimethylol melamine resin, trimethylol trimethoxymethyl melamine resin, and the like. Commercially available products include MA-1 and MA-204 (Sumitomo Bakelite Co., Ltd., both trade names), Bekkamin MA-S, Bekkamin APM, and Bekkamin J-101 (Dainippon Ink Chemical Co., Ltd.). , All of which are trade names), Euroid 344 (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.), Oshika Resin M31 and Oshika Resin PWP-8 (product names of Oshika Promotion Co., Ltd., both trade names). However, it is not limited to these.

  As a melamine compound, it is preferable that the functional group equivalent shown by the value which divided molecular weight by the number of functional groups in 1 molecule is 50-300. Here, the functional means a methylol group and / or an alkoxymethyl group. If this value exceeds 300, the cured density is small and a high strength cannot be obtained. If the amount of the melamine compound is increased, the coating property is lowered. If the curing density is low, scratches are likely to occur. Moreover, when the grade to harden | cure is low, the force holding an electroconductive metal oxide will also fall. If the functional group equivalent is less than 50, the curing density is increased, but the transparency is impaired, and even if the amount is reduced, it does not improve. The addition amount of the aqueous melamine compound is 0.1 to 100% by mass, preferably 10 to 90% by mass with respect to the polymer.

If necessary, the antistatic layer can be used in combination with a matting agent, a charge adjusting agent, a surfactant, a slipping agent and the like. As the matting agent, an oxide such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, more preferably 0.2 μm to 0.5 μm, a polymer such as polymethyl methacrylate and polystyrene, A copolymer etc. are mentioned. The preferred amount of matting agent is ^{2mg / m 2 ~15mg / m 2} .

  Examples of the charge control agent include surfactants described later, polymers containing fluorine atoms, inorganic salts, and organic salts. In particular, surfactants and polymers containing fluorine atoms, salts containing tetraalkylammonium ions, and the like are preferably used.

  Examples of the surfactant include arbitrary anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Examples of the slip agent include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

  The thickness of the antistatic layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior. A surface layer is preferably provided on the antistatic layer. The surface layer is provided mainly for improving the slipping property and scratch resistance and for assisting the detachment preventing function of the conductive metal oxide particles of the antistatic layer.

  Examples of the material for the surface layer include (1) wax, resin and rubber-like ones or copolymers of 1-olefinic unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Products (for example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and propylene / 1-butene copolymer), (2) A rubbery copolymer of two or more kinds of the 1-olefin and a conjugated or non-conjugated diene (for example, an ethylene / propylene / ethylidene norbornene copolymer, an ethylene / propylene / 1,5-hexadiene copolymer, and Isobutene / isoprene copolymer), (3) a copolymer of 1-olefin and conjugated or non-conjugated diene (for example, ethylene / Tadiene copolymers and ethylene / ethylidene norbornene copolymers), (4) 1-olefins, especially copolymers of ethylene and vinyl acetate and complete or partially saponified products thereof, and (5) 1-olefins alone or copolymerized. Examples thereof include, but are not limited to, a graft polymer obtained by grafting the above conjugated or non-conjugated diene or vinyl acetate onto a polymer, and a completely or partially saponified product thereof. The above compound is described in JP-B-5-41656.

  Among these, polyolefins having a carboxyl group and / or a carboxylate group are preferable. Usually used as an aqueous solution or aqueous dispersion.

  Water-soluble methylcellulose having a methyl group substitution degree of 2.5 or less may be added to the surface layer, and the addition amount is preferably 0.1 to 40% by mass with respect to the total binder forming the surface layer. The water-soluble methylcellulose is described in JP-A-1-210947.

  The surface layer may be formed on the antistatic layer by a well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, or extrusion coating. It can form by apply | coating the coating liquid (aqueous dispersion or aqueous solution) containing etc.

  The thickness of the surface layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior.

  The pH of the film in the silver halide color photographic light-sensitive material of the present invention is preferably 4.6 to 6.4, and more preferably 5.5 to 6.5. When the coating pH is higher than 6.5 in a long-time sample, the sensitization of the cyan image and the magenta image due to safelight irradiation is large. Conversely, when the coating pH is lower than 4.5, the photosensitive material is exposed. The yellow image density changes greatly with respect to the time change until development. Either case is a practical problem.

  The coating pH in the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic layers obtained by coating the coating solution on the support and does not necessarily match the pH of the coating solution. The coating pH can be measured by the following method as described in JP-A-61-245153. That is, (1) 0.05 ml of pure water is dropped on the surface of the light-sensitive material coated with the silver halide emulsion. Next, (2) after standing for 3 minutes, the coating pH is measured with a surface pH measurement electrode (GS-165F, trade name, manufactured by Toa Denpa). The coating pH can be adjusted using an acid (for example, sulfuric acid or citric acid) or an alkali (for example, sodium hydroxide or potassium hydroxide) as necessary.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto.

Example 1
[Preparation of support]
Subjecting a primer on the emulsion paint設面side, an acrylic resin layer containing a side opposite to the below of the conductive polymer (0.05g / m ²⁾ and tin oxide fine particles (0.20g / m ²⁾ of emulsion paint設面the A coated polyethylene terephthalate film support (thickness: 120 μm) was prepared.

[Preparation of silver halide emulsion]
-Preparation of blue-sensitive silver halide emulsion-
Large emulsion (BO-01)
(Cube, average sphere equivalent diameter 0.65 μm, sphere equivalent diameter variation coefficient 9%)
It was prepared by adding a silver nitrate aqueous solution and a potassium halide aqueous solution mixed with potassium iodide, sodium chloride and potassium bromide by a control double jet method known in the art. During particle formation, the temperature of the reaction vessel was kept at 60 ° C. and the pAg was kept at 6.6. A silver chloride layer is formed using an aqueous potassium halide solution consisting only of potassium chloride from the start of formation of silver halide grains until 80% of the total silver nitrate used is used, and then 90% of the total silver nitrate is used. Until the silver bromochloride layer is formed using an aqueous potassium halide solution in which potassium bromide and potassium chloride are mixed at a molar ratio of 2:98, and then 95% of the total silver nitrate is used. A silver chloroiodobromide layer is formed using a potassium halide aqueous solution in which potassium chloride, potassium bromide and potassium chloride are mixed at a molar ratio of 3: 2: 95, and then 100% of the total silver nitrate is used. A silver chlorobromide layer was formed using an aqueous potassium halide solution in which potassium iodide, potassium bromide, and potassium chloride were mixed at a molar ratio of 1: 2: 97. An iridium compound was added to the silver bromide layer. The iridium content was adjusted to 4 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.

Blue sensitizing dye (A ′); 3.5 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 2.2 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 1 .9 × 10 ⁻⁵ mol / mol silver Further, gold sulfur was sensitized optimally using chloroauric acid and triethylthiourea.

Medium size emulsion (BM-01)
(Cube, average sphere equivalent diameter 0.52 μm, sphere equivalent diameter variation coefficient 9%)
It was prepared by adding a silver nitrate aqueous solution and a potassium halide aqueous solution mixed with potassium iodide, sodium chloride and potassium bromide by a control double jet method known in the art. During the particle formation, the temperature of the reaction vessel was maintained at 52 ° C. and the pAg was maintained at 6.6. A silver chloride layer is formed using an aqueous potassium halide solution consisting only of potassium chloride from the start of formation of silver halide grains until 80% of the total silver nitrate used is used, and then 90% of the total silver nitrate is used. Until a silver chlorobromide layer is formed using a potassium halide aqueous solution in which potassium bromide and potassium chloride are mixed at a molar ratio of 2:98, and then 100% of the total silver nitrate is used. A silver chloroiodobromide layer was formed using an aqueous potassium halide solution in which potassium iodide, potassium bromide, and potassium chloride were mixed at a molar ratio of 2: 2: 96. An iridium compound was added to the silver chlorobromide layer.

Blue sensitizing dye (A ′); 4.9 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 4.3 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 2 0.7 × 10 ⁻⁵ mol / mol silver Further, gold sulfur was sensitized optimally using chloroauric acid and triethylthiourea.

Small emulsion (BU-01)
(Cube, average sphere equivalent diameter 0.31 μm, coefficient of variation of sphere equivalent diameter 8%)
The BM-01 emulsion was prepared in the same manner as BM-01 except that the grain formation temperature was lowered.

  Sensitizing dyes (A ') to (C') represented by the structural formula described below were added as follows.

Blue sensitizing dye (A ′): 4.5 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (B ′): 4.1 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′): 7 0.0 × 10 ^-5 mol / mol silver -Preparation of red-sensitive silver halide emulsion-
Large size emulsion (RO-01)
(Cube, average sphere equivalent diameter 0.22 μm, sphere equivalent diameter variation coefficient 11%)
It was prepared by adding a silver nitrate aqueous solution and a potassium halide aqueous solution mixed with potassium iodide, sodium chloride and potassium bromide by a control double jet method known in the art. During particle formation, the temperature of the reaction vessel was kept at 60 ° C. and the pAg was kept at 6.6. A silver chloride layer is formed using an aqueous potassium halide solution consisting only of potassium chloride from the start of formation of silver halide grains until 50% of the total silver nitrate used is used, and then 75% of the total silver nitrate is used. Until a silver chlorobromide layer is formed using an aqueous potassium halide solution in which potassium bromide and potassium chloride are mixed at a molar ratio of 6:94, and then 100% of the total silver nitrate is used. A silver chlorobromide layer was formed using an aqueous potassium halide solution in which potassium bromide and potassium chloride were mixed at a molar ratio of 13:87. An iridium compound was added to the silver chloride layer. The iridium content was adjusted to 4 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (D ′) to (F ′) represented by the structural formula described later were added as follows and spectrally sensitized.

Red-sensitive sensitizing dye (D ′): 4.4 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 0.4 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.2 × 10 ⁻⁵ mol / mol silver Further, gold chloride is sensitized optimally using chloroauric acid and triethylthiourea, and then Cpd-71 represented by the structural formula described below is halogenated. 9.4 × 10 ⁻⁴ mol was added per 1 mol of silver.

Medium size emulsion (RM-01)
(Cube, average sphere equivalent diameter 0.17 μm, sphere equivalent diameter variation coefficient 12%)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.

Red-sensitive sensitizing dye (D ′): 7.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.4 × 10 ⁻⁵ mol / mol silver small size emulsion (RU-01)
(Cube, average sphere equivalent diameter 0.12 μm, sphere equivalent diameter variation coefficient 13%)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.

Red-sensitive sensitizing dye (D ′): 8.9 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.2 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.5 × 10 ⁻⁵ mol / mol silver—Preparation of green-sensitive silver halide emulsion—
Large emulsion (GO-01)
(Cube, average sphere equivalent diameter 0.19 μm, sphere equivalent diameter variation coefficient 11%)
It was prepared by adding a silver nitrate aqueous solution and a potassium halide aqueous solution in which sodium chloride and potassium bromide were mixed at a molar ratio of 1:99 by a control double jet method known in the art. K ₂ [IrCl ₆ ] was prepared to be 2 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (G ′) to (J ′) represented by the structural formula described later were added as follows and spectrally sensitized.

Green sensitive sensitizing dye (G ′): 2.6 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 0.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.2 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver Further, using chloroauric acid and triethylthiourea, Gold sulfur sensitized.

Medium size emulsion (GM-01)
(Cube, average sphere equivalent diameter 0.14 μm, sphere equivalent diameter variation coefficient 13%)
GM-01 was prepared in the same manner as GO-01 except that the size was adjusted. Sensitizing dyes (G ′) to (J ′) represented by the structural formula described below were used as follows.

Green sensitive sensitizing dye (G ′): 3.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.3 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.4 × 10 ⁻⁴ mol / mol silver Green-sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver Optimum using chloroauric acid and triethylthiourea Gold sulfur sensitized.

Small emulsion (GU-01)
(Cube, average sphere equivalent diameter 0.094 μm, coefficient of variation of sphere equivalent diameter 19%)
GU-01 was prepared in the same manner as GO-01 except that the size was adjusted. Sensitizing dyes (G ′) to (J ′) represented by the structural formula described below were used as follows.

Green sensitive sensitizing dye (G ′): 5.1 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.7 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.9 × 10 ⁻⁴ mol / mole silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mole silver Further, optimally using chloroauric acid and triethylthiourea Gold sulfur sensitized.

The halogen composition of this emulsion is Br / Cl = 1/99 (molar ratio).

Small emulsion (GU-02)
(Cube, average sphere equivalent diameter 0.094 μm, coefficient of variation of sphere equivalent diameter 19%, halogen composition Br / Cl = 3/97)
Emulsion GU-01 was prepared in the same manner as GU-01 except that the composition of the liquid added was changed so that the halogen composition was Br / Cl = 3/97 (molar ratio) and the size was adjusted. Emulsion GU-02 was prepared.

Small emulsion (GU-03)
(Cube, average sphere equivalent diameter 0.13 μm, sphere equivalent diameter variation coefficient 13%, halogen composition Br / Cl = 25/75)
In the preparation of emulsion GU-01, the composition of the liquid added was changed so that the halogen composition was Br / Cl = 25/75 (molar ratio), the size was adjusted, and K ₂ [RhBr ₅ (H ₂ O )] Was prepared in the same manner as GU-1, except that 5 × 10 ⁻⁸ mol / mol silver was added to the total silver amount.

Small emulsion (GU-04)
(Cube, average sphere equivalent diameter 0.094 μm, coefficient of variation of sphere equivalent diameter 19%, halogen composition Br / Cl = 25/75)
Emulsion GU-04 was prepared in the same manner except that K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)] in the preparation of emulsion GU-03.

Small emulsion (GU-05)
(Cube, average sphere equivalent diameter 0.13 μm, sphere equivalent diameter variation coefficient 13%, halogen composition Br / Cl = 25/75)
Emulsion GU-05 was prepared in the same manner except that K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)] in the preparation of emulsion GU-03.

Small emulsion (GU-06)
(Cube, average sphere equivalent diameter 0.13 μm, sphere equivalent diameter variation coefficient 13%, halogen composition Br / Cl = 3/97)
In the preparation of emulsion GU-02, K ₂ [RhBr ₅ (H ₂ O)] was added in an amount of 5 × 10 ⁻⁸ mol / mol silver to the total silver amount, and the size was adjusted by the grain formation temperature. Emulsion GU-06 was prepared.

Small emulsion (GU-07)
(Cube, average sphere equivalent diameter 0.094 μm, coefficient of variation of sphere equivalent diameter 19%, halogen composition Br / Cl = 3/97)
Emulsion GU-07 was similarly prepared except that K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)] in the preparation of emulsion GU-02.

Small emulsion (GU-08)
(Cube, average sphere equivalent diameter 0.13 μm, sphere equivalent diameter variation coefficient 13%, halogen composition Br / Cl = 3/97)
Emulsion GU-08 was prepared in the same manner except that K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ (H ₂ O)] in the preparation of emulsion GU-06.

Small emulsion (GU-09)
(Cube, average sphere equivalent diameter 0.13 μm, sphere equivalent diameter variation coefficient 13%, halogen composition Br / Cl = 3/97)
In the preparation of emulsion GU-02, K ₂ [RhBr ₅ (H ₂ O)] was added at 5 × 10 ⁻⁸ mol / mol silver based on the total silver amount, and K ₂ [IrCl ₆ ] was changed to K ₂ [IrCl ₅ ]. Emulsion GU-09 was prepared in the same manner except that the change was made to (5-methylthiazole)] and the grain formation temperature and the amounts of various compounds were changed relative to GU-02.

[Preparation of dye solid fine particle dispersion]
The methanol wet cake of the compound (HD-1) was weighed so that the net amount of the compound was 240 g, 48 g of the following compound (Pm-1) was weighed as a dispersion aid, and water was added to make 4000 g. 'Flow-through sand grinder mill (UVM-2)' (manufactured by IMEX K.K.) is filled with 1.7 liters of zirconia beads (0.5 mm diameter), the discharge rate is 0.5 liter / min, and the peripheral speed is 10 m / s. For 2 hours. Thereafter, the dispersion was diluted so that the compound concentration was 3% by mass, and a compound (Pm-1) represented by the following structural formula was added by 3% by mass with respect to the dye (referred to as Dispersion A). The average particle size of this dispersion was 0.45 μm.

  Further, a dispersion containing 5% by mass of the compound (HD-2) (referred to as Dispersion B) was obtained in the same manner.

[Preparation of Sample 101]
Each layer having the composition as shown below was coated on the support in a multilayer manner to prepare Sample 101 which was a multilayer color photographic light-sensitive material.

-Layer structure-
The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion coating amount represents a silver equivalent coating amount. Further, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.

[Layer structure of sample 101]
Support / first polyethylene terephthalate film (halation-preventing layer (non-photosensitive hydrophilic colloid layer))
Gelatin 1.03
Dispersion A (as dye coating amount) 0.10
Dispersion B (as dye coating amount) 0.03.

Second layer (blue sensitive silver halide emulsion layer)
3: 1: 6 mixture of silver chlorobromide emulsion BO-01, emulsion BM-01, and emulsion BU-01 (silver molar ratio) 0.57
Gelatin 2.71
Yellow coupler (ExY ') 1.19
(Cpd-41) 0.0006
(Cpd-42) 0.01
(Cpd-43) 0.05
(Cpd-44) 0.003
(Cpd-45) 0.012
(Cpd-46) 0.001
(Cpd-54) 0.08
(Cpd-65) 0.02
Solvent (Solv-21) 0.26.

Third layer (color mixing prevention layer)
Gelatin 0.59
(Cpd-49) 0.02
(Cpd-43) 0.05
(Cpd-53) 0.005
(Cpd-61) 0.02
(Cpd-62) 0.03
Solvent (Solv-21) 0.06
Solvent (Solv-23) 0.04
Solvent (Solv-24) 0.002.

Fourth layer (red-sensitive silver halide emulsion layer)
2: 2: 6 mixture of silver chlorobromide emulsion RO-01, emulsion RM-01 and emulsion RU-01 (silver molar ratio) 0.40
Gelatin 2.79
Cyan coupler (ExC ') 0.80
(Cpd-47) 0.06
(Cpd-48) 0.06
(Cpd-50) 0.03
(Cpd-53) 0.03
(Cpd-57) 0.05
(Cpd-58) 0.01
(Cpd-60) 0.02
Solvent (Solv-21) 0.53
Solvent (Solv-22) 0.28
Solvent (Solv-23) 0.04.

5th layer (color mixing prevention layer)
Gelatin 0.56
(Cpd-49) 0.02
(Cpd-43) 0.05
(Cpd-53) 0.005
(Cpd-62) 0.03
(Cpd-64) 0.002
Solvent (Solv-21) 0.06
Solvent (Solv-23) 0.04
Solvent (Solv-24) 0.002.

Sixth layer (green sensitive silver halide emulsion layer)
Silver chlorobromide emulsion GO-01, emulsion GM-01, emulsion GU-01
Mixture ratio of 1: 2: 7 (silver molar ratio) 0.54
Gelatin 1.66
Magenta coupler (ExM ') 0.73
(Cpd-49) 0.013
(Cpd-51) 0.001
Solvent (Solv-21) 0.15.

7th layer (protective layer)
Gelatin 0.97
Acrylic resin (average particle size 2 μm) 0.002
(Cpd-55) 0.005
(Cpd-56) 0.08
(Cpd-59) 0.03.

  The compounds used here are shown below.

Sample 101 was produced as described above.
<Preparation of Samples 102 to 109>
Next, Samples 102 to 109 were prepared in exactly the same manner except that the emulsion GU-01 in the sixth layer was changed to GU-02 to GU-09 in the preparation of the sample 101, respectively.

<Preparation of Samples 111 to 119>
Furthermore, samples 111 to 119 of photosensitive materials differing only in that the surfactant (Cpd-55) in the seventh layer was replaced with (FS-1) in the photosensitive material 101 to 109 with an equal mass.

<Test and evaluation>
The samples 101 to 109 and 111 to 119 were subjected to the following evaluation in order to evaluate the color unevenness of uniform solid gray exposure by exposure using a digital micromirror device. As a printer, the printer having the structure and sequence described in this section of the best mode for carrying out the invention was manufactured and used. This printer can create ornamental print samples from digital data, and if you design the system so that exposure can be performed in conjunction with the projector, you can easily create print samples of your favorite color while looking at the projected image. However, there is a problem in that the density of the obtained image is different in the print surface and color unevenness occurs as shown in the following comparative example.

  In FIG. 5, samples 101 to 109 and 111 to 119 were processed into rolls so that they could be conveyed from the delivery roll 44 to the processor 45, and were exposed, printed, and developed. The development processing was carried out according to the ECP-2 process published by Eastman Kodak Company.

The gray image was printed with a width of 65 mm in the width direction of the sample 101 processed into a roll shape. The density at a density point of 5 mm from both ends in the width direction of the sample is measured with a Macbeth densitometer, and the higher density point is taken as a reference point, and the other point is taken as a test point. A solid exposure image is printed so that the density of the reference point is Y = 0.3 ± 0.03, M = 0.3 ± 0.03, and C = 0.3 ± 0.03 as measured by a Macbeth densitometer. did. Next, the density of the point to be inspected was measured, and the increase / decrease ΔM of the magenta density with respect to the density of the reference point was determined.
The measurement results are shown in the table below.

  From the table, the photosensitive material using the compound of the present invention has at least one micromirror array in which a plurality of micromirrors are arranged in a line, and each micromirror is in an effective reflection state according to 1-bit mirror driving data. And a micromirror device that can be displaced into an ineffective reflection state, and a light source that irradiates light to the micromirror device, and the reflected light from each micromirror that has entered the effective reflection state is projected onto a photosensitive material to produce an image. It can be seen that a high-efficiency printing system can be provided by solving the problem of color unevenness of the printer that exposes the image.

  Furthermore, it can be seen that the sample using (FS-1) can obtain a high-quality image with less unevenness in color.

The wave form diagram which shows the relationship between the operation state of a micromirror, and a LED lighting signal. An explanatory plan view showing a digital micromirror device. Explanatory drawing which shows a micromirror structure. Explanatory drawing which shows operation | movement of a micromirror. Schematic diagram of a color digital printer. Explanatory drawing which shows the projection state to the photographic paper by a digital micromirror device. The wave form diagram which shows the lighting state of each color LED device at the time of recording 1 line. An explanatory plan view showing an example of a digital micromirror device having two micromirror arrays. Explanatory drawing which shows the recording state of the photographic paper at the time of using the digital micromirror device of FIG. The wave form diagram which shows the relationship between the operation state of a micromirror when using the digital micromirror device of FIG. 8, and a LED lighting signal. FIG. 3 is an explanatory plan view showing an example of a digital micromirror device that performs exposure of one color every time one line of photographic paper is sent. Explanatory drawing which shows the exposure state by the digital micromirror device of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10, 50, 60 ... Digital micromirror device 11, 51, 52, A1-A3, B1-B3 ... Micromirror array 12 ... Micromirror 20-22 ... LED device 29 ... Lights Control circuit 30 ... Controller 41 ... Printing paper

Claims (7)

A micromirror device having at least one micromirror array in which a plurality of micromirrors are arranged in a line, each micromirror being displaceable between an effective reflection state and an invalid reflection state according to 1-bit mirror drive data And a light source for irradiating light to the micromirror device, a printer for projecting the reflected light from each micromirror in an effective reflection state onto the photosensitive material and exposing the image, and a silver halide color photographic photosensitive material In which the silver halide color photographic light-sensitive material is provided on a transmissive support with at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and blue-sensitive silver halide, respectively. A silver halide color photographic light-sensitive material for movies having an emulsion layer, wherein at least one of the silver halide emulsion layers has a silver chloride content. Movie halogenation containing 5 mol% or more of silver halide emulsion, and the silver halide emulsion contains at least one metal complex represented by the following general formula (D1) and general formula (D2) An image forming method, which is a silver color photographic light-sensitive material.
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
(In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, X ^D1 represents a halogen ion. L ^D1 is an arbitrary different from X ^D1 Wherein n represents 3, 4, 5 or 6, and m represents the charge of the metal complex and represents 4-, 3-, 2-, 1-, 0 or 1+, where A plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, they may be the same or different, provided that the metal complex represented by the general formula (D1) (There is no or no CN ion.)
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
(In the general formula (D2), X ^D2 represents a halogen ion or a pseudo-halogen ion (excluding a cyanate ion), and L ^D2 represents an arbitrary ligand different from X ^D2. N is 3, 4 Or 5, wherein m is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2 may be the same or different from each other. Well, when there are multiple ^LD2s , these may be the same or different.) 2. The metal complex represented by the general formula (D1) is contained in silver halide grains in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol per mol of silver. Image forming method. The image forming method according to claim 1, wherein the metal complex represented by the general formula (D1) is a metal complex represented by the following general formula (D1A).
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
(In the general formula (D1A), M ^D1A represents Re, Ru, Os or Rh, X ^D1A represents a halogen ion, L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, M ^{When D1A} is Rh, it represents H ₂ O, OH or O. n represents 3, 4, 5 or 6, m is the charge of the metal complex, and 4-, 3-, 2-, 1-, Represents 0 or 1+, wherein a plurality of X ^D1A may be the same as or different from each other, and when a plurality of L ^D1A are present, they may be the same or different; The image forming method according to claim 1, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2A).
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
(In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), L ^D2A represents an arbitrary inorganic ligand different from X ^D2A , n is 3, 4 or 5 and m is the charge of the metal complex and represents 5-, 4-, 3-, 2-, 1-, 0, or 1+, where a plurality of X ^D2A may be the same or different from each other ^Or when there are a plurality of L ^{D2A s} , these may be the same or different.) The image forming method according to claim 1, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2B).
General formula (D2B)
_{^{[IrX D2B n L D2B (6}} -n)] m
(In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding cyanate ion), and L ^D2B has a matrix structure of a chain or cyclic hydrocarbon, or a matrix thereof. Represents a ligand in which a carbon or hydrogen atom in a part of the structure is replaced with another atom or atomic group, n represents 3, 4 or 5, m represents the charge of the metal complex, and 5-4 -, 3-, 2-, 1-, 0 or 1+, wherein a plurality of X ^D2Bs may be the same as or different from each other, and when a plurality of L ^D2Bs are present, they may be the same or different. .) The image forming method according to claim 1, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2C).
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
(In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand, and has at least one nitrogen atom in the ring skeleton. Represents a ligand containing at least one sulfur atom, and may have an optional substituent on a carbon atom in the ring skeleton, n represents 3, 4 or 5, and m represents the charge of the metal complex. 5-, 4-, 3-, 2-, 1-, 0, or 1+, wherein a plurality of X ^D2Cs may be the same as or different from each other, and when a plurality of L ^D2Cs are present, May be the same or different.)   7. The image according to claim 1, further comprising: a light source modulation unit that changes a lighting time of a light source that irradiates a micromirror that is held in an effective reflection state as a light source of the printer. Forming method.

Images