JP2004310080A - Exposure apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an exposure apparatus having excellent beam quality and a sufficient extinction ratio. <P>SOLUTION: In the exposure apparatus 10, a beam 40 emitting from an emitting point 16 of a laser diode (LD) 12 is restricted by a first slit 20 formed in a first slit plate 18. The first slit 20 restricts the beam in the direction (shown as an arrow V) orthogonal to the active layer 14 of the LD 12. The apparatus is equipped with a moving mechanism 22 to allow the first slit plate 18 to move in the direction of the arrow V. When the beam is restricted by disposing the first slit plate 18 near the emitting point 16, which means the beam is restricted near the emitting point 16, namely the point where the beam spot is rendered to the smallest, only flare light can be efficiently shut off because the object point of the flare light differs from that of the beam. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an exposure apparatus.

  Conventionally, in a semiconductor laser emitting light in a long wavelength red to infrared region, a light beam limiting means (aperture) is provided after a coupling lens that converts a beam emitted from a laser crystal into substantially parallel light or convergent light, or a cup. The light beam is limited by the aperture of the ring lens to shape the beam.

  However, GaN-based semiconductor lasers that emit blue light that have been put into practical use in recent years use materials that do not absorb blue light, such as sapphire and SiC (silicon carbide), which are substrates.

  For this reason, a phenomenon has occurred in which reflected light reflected inside the LD chip that emits light is emitted as stray light to the outside, or returns to the vicinity of the active region and affects the laser oscillation state. This causes problems such as poor beam quality in the direction perpendicular to the PN junction surface of the LD chip and insufficient extinction ratio. As a result, when this blue semiconductor laser is used as an exposure light source, image quality deteriorates. When used as a reading light source of a recording device, it may cause erroneous detection.

  Further, when used as an exposure light source of an image recording apparatus that records an image by modulating the exposure intensity according to the image signal, the contrast of light and shade cannot be sufficiently obtained because the extinction ratio is insufficient.

  As shown in FIG. 12A, the beam 110 emitted from the LD 102 becomes parallel light by the coupling lens 104 and forms an image at the focal point 108 by the lens 106. However, stray light from the inside of the LD 102 becomes flare light 112 and becomes the PN of the LD 102. The beam quality in the direction perpendicular to the joint surface (arrow V) is degraded, and sufficient contrast cannot be obtained.

  On the other hand, as shown in FIG. 12B, even if the slit 114 is inserted behind the coupling lens 104 to limit the flare light 112, the object point of the flare light 112 is different from the laser emission point, and the surface of the LD. However, since the flare light 112 passes through the opening of the slit 114, it is difficult to remove only the flare light 112.

  Also, as shown in FIG. 12C, a mechanism has been devised in which a part of the beam is guided to the sensor 118 by the beam splitter 116, the light amount is detected, and the drive voltage of the LD 102 is feedback-controlled by the controller 120. This is because the light quantity of the LD 102 is monitored in real time for the purpose of stabilizing the light quantity of the beam. However, since flare light that is not received by the light receiving surface of the sensor 118 exists at this time, the light quantity on the image plane and the sensor 118 The relationship between the amounts of received light deviates from linearity, and linearity is lost.

Conventionally, a structure is disclosed in which a diaphragm is fixed to a laser light source with an adhesive or the like, and an angle of an aperture of the diaphragm is fixed with respect to the laser light source (see, for example, Patent Document 1). However, when using an LD having a plurality of light emitting points, the position of the light emitting points and the angle of the aperture opening are accurately maintained and are not a countermeasure against stray light.
Japanese Patent Laid-Open No. 11-58829 (first page, FIG. 1)

  In view of the above facts, an object of the present invention is to provide an exposure apparatus having excellent beam quality and a sufficient extinction ratio.

  The exposure apparatus according to claim 1, wherein the exposure apparatus uses a GaN-based blue semiconductor laser as a light source. The exposure apparatus limits a passing light beam between an active layer of the semiconductor laser and a coupling lens closest to the active layer. Limiting means is provided, and the limiting direction of the first limiting means is a direction orthogonal to the active layer of the semiconductor laser.

  In the invention having the above configuration, the object points generated by the laser beam and the stray light are different in the direction orthogonal to the active layer, and are located on the crystal surface and inside the crystal, respectively. By limiting the light flux and limiting the luminous flux, stray light can be separated and blocked.

  The exposure apparatus according to claim 2 is characterized in that the first restricting means is movable in a restricting direction relative to the light source.

  In the invention having the above-described configuration, the slit or the like as the restricting means can be moved in the restricting direction, that is, the direction orthogonal to the active layer, so that the optimum position can be provided. It is also possible to fix the limiting means and move the light source.

  The exposure apparatus according to claim 3 is provided with a second restricting means for restricting a passing light beam after the coupling lens, and the restricting direction of the second restricting means is a direction along the active layer of the laser crystal. Features.

  In the invention with the above-described configuration, the shape of the focused beam at the time of LED emission, which was not a problem at the time of laser oscillation, can be shaped to a more ideal shape.

  The exposure apparatus according to claim 4 is characterized in that the second restricting means is movable in the restricting direction.

  In the invention with the above configuration, the slit or the like, which is the limiting means, can be moved in the limiting direction, that is, the direction along the active layer, so that it can be provided at an optimal position.

6. The exposure apparatus according to claim 5, wherein the opening width in the limiting direction of the first limiting means is D, the distance from the light emitting surface of the active layer to the first limiting means is L, and the beam spreads from the light emitting surface. When the angle is α
D / {2L · tan (α / 2)} ≦ 2.0
It is the structure which satisfies these.

  In the invention with the above configuration, if the kick rate t of the beam by the slit is t = D / W, and W = 2L · tan (α / 2), the kick rate is suppressed to t ≦ 2.0. The side lobe strength (unnecessary component) can be suppressed to 3 to 4%.

7. The exposure apparatus according to claim 6, wherein the numerical aperture of the coupling lens closest to the light emitting surface of the active layer of the blue semiconductor laser is NA, and the beam from the light emitting surface is an exposure apparatus that uses a GaN blue semiconductor laser as a light source. When the spread angle of α is α,
NA · tan (α / 2) ≦ 2.0
In the invention of the above configuration, instead of separately providing a limiting means such as a slit, the luminous flux is reduced by limiting the numerical aperture of the coupling lens closest to the light emitting surface of the active layer. Can be limited.

8. The exposure apparatus according to claim 7, wherein a GaN-based blue semiconductor laser is used as a light source, an image is formed on a photosensitive material using silver halide by irradiation light from the GaN-based blue semiconductor laser, and the GaN-based blue semiconductor In an exposure apparatus that performs gradation expression of the image by controlling a driving current of a laser and modulating a light emission intensity of the irradiation light, a light emitting point of the active layer of the GaN-based blue semiconductor laser and a cup closest to the light emitting point A first restricting means for restricting a passing light beam is provided between the ring lens and the restricting direction of the first restricting means is a direction orthogonal to the active layer of the GaN-based blue semiconductor laser, and the first restricting means The opening width in the limiting direction of the means is D, the distance from the light emitting surface of the active layer to the first limiting means is L, and the beam divergence angle from the light emitting point is α. Come,
D / {2L · tan (α / 2)} ≦ 1.8
It is the structure which satisfies these.

  In the invention having the above-described configuration, the dynamic range of the exposure amount required to achieve the contrast of light and shade necessary for reproducing a photographic image using a general silver salt light-sensitive material can be reduced by using a limiting means such as a slit. By removing, about 1.5 can be secured.

The exposure apparatus according to claim 8 uses a GaN-based blue semiconductor laser as a light source, forms an image on a photosensitive material using silver halide by irradiation light from the GaN-based blue semiconductor laser, and the GaN-based blue semiconductor. In an exposure apparatus that performs gradation expression of the image by controlling the drive current of the laser and modulating the emission intensity of the irradiation light, the aperture of the coupling lens closest to the emission point of the active layer of the GaN-based blue semiconductor laser When the number is NA and the beam divergence angle from the light emitting point is α,
NA · tan (α / 2) ≦ 1.8
It is the structure which satisfies these.

  In the invention with the above configuration, the coupling lens closest to the light emitting surface has a dynamic range of the exposure amount required to achieve the contrast of light and shade necessary when reproducing a photographic image using a general silver salt photosensitive material. By limiting the numerical aperture, it is possible to secure about 1.5 by removing stray light.

  The exposure apparatus according to claim 9 is characterized in that a predetermined driving current is continuously applied to the GaN-based blue semiconductor laser and the GaN-based blue semiconductor laser emits light in the LED region even in the absence of an image signal.

  In the invention having the above-described configuration, a pre-light emission state is obtained by constantly applying a driving current to the GaN-based blue semiconductor laser, so that the response at the time of inputting an image signal, that is, the rising characteristic can be improved.

  11. The exposure apparatus according to claim 10, wherein the light-sensitive material using silver halide is a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red light sensitive material on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one layer of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, the total amount of gelatin coated in the photographic constituent layer is 3 g / m @ 2. A silver halide color photograph containing a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less and a silver chloride content of 90 mol% or more in the yellow color developing blue-sensitive silver halide emulsion layer of 6 g / m 2 or less. It is a photosensitive material.

  In the invention of the above configuration, a color photographic image is reproduced by using a silver halide color photographic light-sensitive material that is suitable for rapid processing and has a rapid development progress even in digital exposure such as laser scanning exposure and can obtain a high gradation. By removing stray light, it is possible to secure a dynamic range of the exposure amount required to achieve the contrast of light and shade required at the time.

  12. The exposure apparatus according to claim 11, wherein the light-sensitive material using silver halide is a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red light sensitive material on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one layer of a light-sensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, the total amount of coated silver in the photographic constituent layer is 0.2 g. Halogen containing a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less and a silver chloride content of 90 mol% or more in the yellow coloring blue-sensitive silver halide emulsion layer. It is a silver halide color photographic light-sensitive material.

  In the invention of the above configuration, a color photographic image is reproduced by using a silver halide color photographic light-sensitive material that is suitable for rapid processing and has a rapid development progress even in digital exposure such as laser scanning exposure and can obtain a high gradation. By removing stray light, it is possible to secure a dynamic range of the exposure amount required to achieve the contrast of light and shade required at the time.

  13. The exposure apparatus according to claim 12, wherein the light-sensitive material using silver halide is a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red light sensitive material on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one layer of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, the total amount of gelatin coated in the photographic constituent layer is 3 g / m @ 2. 6 g / m 2 or less, and the total coating amount of silver in the photographic composition layer is 0.2 g / m 2 or more and 0.5 g / m 2 or less, equivalent to a sphere in the yellow color developing blue-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material comprising a silver halide emulsion having a diameter of 0.6 μm or less and a silver chloride content of 90 mol% or more.

  In the invention of the above configuration, a color photographic image is reproduced by using a silver halide color photographic light-sensitive material that is suitable for rapid processing and has a rapid development progress even in digital exposure such as laser scanning exposure and can obtain a high gradation. By removing stray light, it is possible to secure a dynamic range of the exposure amount required to achieve the contrast of light and shade required at the time.

  Since the present invention has the above-described configuration, it was possible to obtain an exposure apparatus excellent in beam quality, having a sufficient extinction ratio, and matching the characteristics of the silver salt photosensitive material.

  FIG. 1 shows a perspective view of an exposure apparatus according to the first embodiment.

  As shown in FIG. 1, in the exposure apparatus 10, a beam 40 emitted from a light emitting point 16 of a laser diode (hereinafter referred to as LD) 12 is first limited by a first slit 20 provided in a first slit plate 18. At this time, the first slit 20 includes a moving mechanism 22 that restricts the light flux in a direction (arrow V) orthogonal to the active layer 14 of the LD 12 and that allows the first slit plate 18 to move in the arrow V direction. As shown in FIG. 1, the moving mechanism 22 is provided with a long hole in the direction of arrow V as a simpler mechanism in addition to a mechanism composed of a driving device in which a stepping motor is combined with a rack and pinion gear. May be movable in the direction of arrow V along the long hole, and may be screwed at an appropriate position. At this time, if a scale is engraved in the elongated hole, the position reproducibility is improved.

  In addition to the moving mechanism 22, a moving mechanism (not shown) that can move the first slit plate 18 in the direction of arrow H is also provided, and the moving mechanism can also be moved in a direction orthogonal to the arrow V.

  Alternatively, the first slit plate 18 may be fixed and the LD 12 may be moved.

  The beam 40 from which stray light has been removed by the first slit 20 passes through a coupling lens (hereinafter referred to as CL) 24 to become parallel light and is guided to the second slit 28.

  The second slit 28 provided in the second slit plate 26 restricts the light flux in the direction along the active layer 14 of the LD 12 (arrow H) and allows the second slit plate 26 to move in the arrow H direction. It has. This moving mechanism 30 is also provided with a long hole in the direction of arrow H as a simpler mechanism in addition to a mechanism comprising a driving device in which a stepping motor is combined with a rack and pinion gear as shown in FIG. 26 may be configured to be movable in the direction of arrow H along the elongated hole and screwed at an appropriate position.

  In addition to the moving mechanism 30, a moving mechanism (not shown) that can move the second slit plate 26 in the direction of the arrow V is also provided, and can move in the direction orthogonal to the arrow H.

  The beam 40 shaped by the second slit 28 is focused on an image plane (not shown) by the second lens 32.

  FIG. 2 is a side view showing the effect of the first slit according to the first embodiment.

  In FIG. 2A, the first slit 20 is not provided, so that the flare light 42 reflected inside the LD 12 reaches the vicinity of the focal point 44 and degrades the beam quality.

  On the other hand, in FIG. 2B, a first slit plate 18 is provided in the vicinity of the light emitting point 16 to limit the light flux. At this time, since the object point is different between the beam 40 and the flare light 42, if the light flux is limited in the vicinity of the light emitting point 16, that is, near the point where the beam spot is the smallest, the flare light 42 as shown in FIG. Can be cut off efficiently.

  This improvement in beam quality is shown in FIG.

  FIG. 3 shows a graph showing the effect of the first slit according to the first embodiment.

  3A and 3B show the distance from the optical axis and the intensity of the laser beam when the first slit 20 having a slit width of 0.5 mm is not provided and when it is provided. The horizontal axis indicates the distance (μm) from the optical axis, and the vertical axis indicates the intensity of the laser beam.

  In FIG. 3A, since the first slit 20 is not provided and there is no means for blocking stray light from the LD 12 to the CL 24, flare light 42 which is an unnecessary component, that is, the side lobe intensity is about 10%.

  In FIG. 3B, the first slit 20 having a slit width of 0.5 mm is provided, and the flare light 42 is blocked in the vicinity of the light emitting point 16 as shown in FIG. 2B, so that the side lobe intensity is suppressed to about 3%. It has been.

  In this case, side lobes are generated due to the diffraction effect of kicking due to the restriction by the first slit 20, but as a result of effectively blocking the flare light 42 generated inside the LD 12, as shown in FIG. The beam quality is improved.

Here, when the width of the first slit 20 is D, the spread angle of the beam emitted from the LD 12 is α, and the distance from the light emitting surface of the active layer of the LD to the first slit is L, the beam width W at the slit position. Is W = 2L · tan (α / 2)
It becomes. At this time, the kick rate t in the first slit 20 is t = D / W
4 (a) to 4 (d) show beam quality fluctuations when the kick rate t is changed from 2.4 to 1.8. The vertical axis indicates the intensity, the horizontal axis indicates the distance from the optical axis, the intensity of the main beam appears in the center, and the sidelobe intensity, which is an unnecessary light component, appears on both sides of the main peak.

  In FIG. 4 (a), the side lobe strength is about 22% at a kick rate t = 2.4, whereas in FIG. 4 (b), the side lobe strength is about 9% at a kick rate t = 2.2. In FIG. 4 (c), the side lobe strength can be reduced to about 3% at a kick rate t = 2.0. However, in FIG. 4D, even when the kick rate t = 1.8, the side lobe intensity is still about 3%, and no improvement is seen even when t = 2.0 in FIG. 4C.

From this, it can be seen that the slit kick rate effective for reducing the side lobe strength is t ≦ 2.0. In this example, as a slit width setting that reduces the side lobe intensity and does not reduce the main beam intensity,
t = D / W = D / {2L · tan (α / 2)} ≦ 2.0
It is characterized by satisfying the following relationship.

Further, as the light beam limiting means, the numerical aperture (NA) of the CL 24 may be limited instead of providing the first slit 20. At this time,
NA = D / 2L
Because
NA / tan (α / 2) ≦ 2.0
The object of the present application can also be achieved by adopting a configuration that satisfies this relationship.

  By the way, when the focal length of the CL 24 is about several millimeters, the beam diameter at the first slit 20 is very thin, about 0.5 to 1.0 mm, and the slit width D of the first slit 20 is also about 0.5 mm. . For this reason, in order to obtain a beam that is symmetrical with respect to the optical axis and has few side lobes, it is necessary to adjust the relative position between the first slit 20 and the beam optical axis in units of 10 μm. In the present embodiment, the first slit plate 18 can be moved in the light beam restricting direction by the moving mechanism 22 so that the position of the first slit 20 can be adjusted.

  For example, as shown in FIG. 5, when the center of the first slit 20 is deviated from the optical axis, the side lobe intensity increases even with a deviation of about 50 μm, and the beam quality deteriorates. In FIG. 5A, the amount of deviation is 0 μm, while in FIG. 5B, the side lobe intensity increases from about 3% to about 5% when the amount of deviation is 50 μm.

  FIG. 6 shows a graph showing the effect of the second slit according to the first embodiment.

  With respect to the beam 40 emitted from the LD 12, the beam quality can be maintained by setting the first slit 20 or limiting the numerical aperture of the CL 24 in the laser oscillation region. Cannot be shaped. The effect of stray light that can ignore the influence of the beam during LED emission cannot be ignored because the intensity is relatively weak compared to the laser during laser oscillation.

  That is, when the light side limiting means is not provided after CL 24, the intensity distribution is as shown in FIG. 6A, and the side lobe intensity reaches 20%, so that good beam quality cannot be obtained. Therefore, in this embodiment, the second slit 28 is provided between the CL 24 and the second lens 32 to perform beam shaping. Here, when the opening width D of the first slit is 0.5 mm and the focal length of the CL 24 is 8.0 mm, the side lobe is inserted as shown in FIG. 6B by inserting the second slit 28 having an opening width of 1 to 2 mm. The strength could be suppressed to 5% or less.

  Similarly to the first slit 20, the second slit 28 can be adjusted in position by moving the second slit plate 26 in the restricting direction (arrow H) by the moving mechanism 30. It was.

  Since the present embodiment is configured as described above, an exposure apparatus that has excellent beam quality and a sufficient extinction ratio can be obtained.

  In addition, since the amount of light of the beam is monitored in real time by the sensor for stable driving of the LD and the feedback control is performed, stray light that affects the sensor can be cut, so that more accurate drive control can be performed.

  FIG. 7 shows a characteristic curve of a general silver salt photosensitive material.

  In the silver halide light-sensitive material, the color density D changes as the vertical axis changes with respect to the incident light amount logE shown on the horizontal axis, so that it is necessary to secure a dynamic range that is a light / dark difference in exposure amount in order to obtain a good image. There is. The dynamic range of the exposure amount necessary to reproduce the contrast of light and shade required for a photographic image is generally about 1.5.

  Therefore, in the second embodiment of the present application, it is an object to ensure a dynamic range of exposure amount 1.5 on the assumption that a silver salt photosensitive material is used.

  FIG. 8 shows a graph showing the effect of the first slit according to the second embodiment.

  FIG. 8A shows the relationship between the drive current to the LD 12 and the amount of light in an exposure apparatus that does not include the first slit 20. In this case, since the first slit 20 is not present, there is a large amount of stray light. As a result, the amount of light in the LED light emitting region is large, so that a dynamic range of only about 1.0 can be secured in the laser oscillation region.

  In addition, since the LD 12 cannot be used at the maximum driving voltage due to the risk of life or destruction of the LD 12, the actual dynamic range becomes narrower.

  In contrast, in the present embodiment, the first slit 20 is provided between the LD 12 and the CL 24, and the stray light is blocked by restricting the light beam at a position close to the light emitting point 16 of the LD 12, and the light amount in the LED light emitting region is totally reduced. As a result, the dynamic range from the laser oscillation region to the LED light emission region is expanded.

  When the first slit 20 is used to block stray light, as shown in FIG. 8B, the amount of light in the LED light emitting region is greatly reduced, and the dynamic range can be expanded by about one digit.

  The effect of the first slit 20 will be described below with specific numerical values.

FIG. 9 shows the relationship between the LD kicking rate t (horizontal axis) and the slit passing rate T (vertical axis) of the LD component and the LED component. If the aperture width of the slit is D and the beam diameter at the slit is W, t = D / W
It is represented by

  As shown in FIG. 9, when the kick rate t exceeds 2.0, the light shielding rate of the LED component is too low and a clear effect cannot be expected. Further, when the kick rate t is 1.5 or less, the amount of laser light decreases greatly, and the adverse effect due to diffraction increases. Therefore, it can be determined that the range of the kick rate t is about 1.5 to 2.0.

  The dynamic range of the amount of light required to reproduce the contrast of a photograph using a silver halide photosensitive material cannot increase the amount of light when the maximum amount of light (LD oscillation) is driven as described above. ) Ensure by reducing the amount of light during driving. In consideration of maintaining the beam quality, it is desirable to secure a dynamic range necessary in the LD oscillation region as much as possible.

Assuming that the dynamic range of the LD oscillation range is Emax and the laser oscillation range is Eth,
LogE = Log (Emax / Eth)
It can be expressed as Here, the relationship between LogE and kicking rate t is as follows: if the beam divergence angle from LD 12 is α, t = D / W = D / {2L · tan (α / 2)}
As shown in FIG. As shown in FIG. 10, if a slit having a kick rate of 1.87 is used, a dynamic range of 1.5 can be secured in the LD region.

  FIG. 11 shows the relationship between the kick rate t and the dynamic range. That is, the horizontal axis is the kick rate t, and the vertical axis is a dynamic range that can be secured only in the laser oscillation region, as indicated by an arrow in FIG.

Also from FIG. 11, in order to ensure a dynamic range (vertical axis) of 1.5 in the LD oscillation region, the kick rate (horizontal axis) t is 1.8 or less, that is, D / {2L · tan (α / 2 )} ≦ 1.8.

  If the kick rate t is made smaller than necessary, the amount of light in the laser oscillation region will be insufficient, and even if the dynamic range can be secured, the absolute amount of light will not be sufficient for the sensitivity of the silver halide photosensitive material, which will hinder image formation. Therefore, it is necessary to set the kick rate t in consideration of both the dynamic range and the sensitivity.

  By the way, in each of the above embodiments, the LD 12 does not exhibit a predetermined performance at the same time as the power is turned on. In order to obtain the desired performance with the LD 12, it is necessary to set a certain time after the power is turned on, and it is necessary to consider the influence of so-called rising characteristics.

  Therefore, even when the area is outside the image area or the area where the image signal is zero, a predetermined current is passed through the LD 12, and the drive circuit is set so that the LD 12 always emits faint light (so-called pre-emission). The rise characteristic can be improved.

[Silver halide color photographic material]
The silver halide color photographic light-sensitive material used in each of the above embodiments can be constructed as follows.

  The silver halide color photographic light-sensitive material used in each example comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red-sensitive silver halide emulsion on a support. A photographic constituent layer comprising at least one layer and a non-photosensitive hydrophilic colloid layer, and the photographic constituent layer is provided in a specific gelatin coating amount or a specific silver coating amount as described later, The yellow-colored blue-sensitive silver halide emulsion layer contains a specific silver halide emulsion.

The total amount of gelatin coated in the photographic composition layer in the photographic material of the present invention is preferably 3 g / m 2 or more and 6 g / m 2 or less, more preferably 3 g / m 2 or more and 5 g / m 2 or less. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability and residual color, the film thickness of the entire photographic constituent layer is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6. It is preferably 5 μm. The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swelling film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. The total amount of silver applied in the photographic composition layer in the light-sensitive material of the present invention is preferably 0.2 g / m 2 or more and 0.5 g / m 2 or less, preferably 0.2 g / m 2 or more and 0.45 g / m 2 or less. Is more preferable. In the light-sensitive material of the present invention, either the total coated gelatin amount or the total coated silver amount in the photographic constituent layer needs to satisfy the above-mentioned preferable range, and naturally it is best to satisfy both.
[Silver halide emulsion] The silver halide emulsion will be described in detail below. As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific equivalent sphere diameter is used. In particular, in the case of a yellow color developing blue-sensitive silver halide emulsion layer, it is included in the silver halide emulsion. The equivalent spherical diameter of the silver halide grains must be 0.6 μm or less (preferably 0.2 μm or more and 0.6 μm or less), preferably 0.5 μm or less, and 0.4 μm or less. Is more preferable.

  On the other hand, in the case of a magenta-colored green light-sensitive silver halide emulsion layer and a cyan-colored red light-sensitive silver halide emulsion layer, the sphere equivalent diameter of silver halide grains contained in the silver halide emulsion is 0.4 μm or less (preferably 0 .2 μm or more and 0.4 μm or less), more preferably 0.35 μm or less, and most preferably 0.3 μm or less.

  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 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.40 μm, and a sphere equivalent diameter of 0.4 μm. Particles correspond to cubic particles having a side length of about 0.32 μm, particles having a sphere equivalent diameter of 0.35 μm correspond to cubic particles having a side length of about 0.28 μm, and particles having a sphere equivalent diameter of 0.3 μm are about a side length. Corresponds to 0.24 μm cubic particles. The particle shape of this particle is not particularly limited, but is substantially a cubic or tetradecahedral crystal particle having {100} faces (they may have rounded vertices and higher order faces). ), Octahedral crystal grains, and the main surface is preferably composed of tabular grains having an aspect ratio of 2 or more and comprising {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. In the present invention, cubic or tetrahedral particles are more preferable.

  As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific silver halide content is used. In particular, in the case of a yellow color developing blue-sensitive silver halide emulsion layer, a silver halide emulsion The silver chloride content needs to be 90 mol% or more. From the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, and more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, and more preferably 0.5 to 5 mol% in order to increase the development speed of the gradation portion with high contrast by high illumination exposure. The silver iodide content is preferably 0.02 to 1 mol%, more preferably 0.05 to 0.50 mol%, in order to increase the development speed of the gradation portion with high contrast under high illumination exposure. Most preferred is 07 to 0.40 mol%. In particular, in the case of a yellow-colored blue-sensitive silver halide emulsion layer, the silver halide grains in the silver halide emulsion are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above-described halogen composition. On the other hand, in the case of a magenta-colored green light-sensitive silver halide emulsion layer and a cyan-colored red light-sensitive silver halide emulsion layer, it is preferable to have the same silver halide content.

  The silver halide grains in the silver halide emulsion used in the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion used in the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion used in the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion used in the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. . Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion used in the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  Introducing bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion used in the present invention may be carried out by adding a bromide salt or iodide salt solution alone, or Along with the addition of the high chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

  The addition of the bromide salt or iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained. On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  Distribution of bromide or iodide ion concentration in the depth direction in the grain is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.

  The silver halide emulsion used in the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the sphere equivalent diameter of all the particles of the present invention needs to be 20% or less, more preferably 15% or less, and still more preferably 10% 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. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.

  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 grains be silver halide grains as defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

  The specific silver halide grains in the silver halide emulsion used in the present invention preferably contain iridium. As the iridium compound, a 6-coordination complex having 6 ligands and having iridium as a central metal (6-ligand iridium complex) is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of the iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br or I as a ligand is preferred, and Ir comprising all six ligands consisting of Cl, Br or I is preferred. A hexacoordinate complex as a central metal is more preferable. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

Specific examples of the 6-coordination complex in which all six ligands are composed of Cl, Br or I and having Ir as a central metal are given below, but iridium in the present invention is not limited to these.
[IrCl6] 2- [IrCl6] 3- [IrBr6] 2- [IrBr6] 3- [IrI6] 3- As a different preferred embodiment of iridium used in the present invention, Ir having at least one ligand other than halogen or cyan is used. A hexacoordination complex having a central metal is preferred, and a hexacoordination complex having Ir as a central metal having H2O, OH, O, OCN, thiazole or substituted thiazole as a ligand is preferred, and at least one H2O, OH, O, More preferred is a hexacoordinate complex having OCN, thiazole or substituted thiazole as a ligand, and the remaining ligand consisting of Cl, Br or I and having Ir as a central metal. Further, a hexacoordination complex having 1 or 2 5-methylthiazole as a ligand and the remaining ligand of Ir, consisting of Cl, Br or I, as a central metal is most preferable.

The following are specific examples of hexacoordination complexes having at least one H 2 O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand of Cl, Br or I as the central metal. However, iridium in the present invention is not limited to these.
[Ir (H2O) Cl5] 2- [Ir (H2O) 2Cl4]-[Ir (H2O) Br5] 2- [Ir (H2O) 2Br4]-[Ir (OH) Cl5] 3- [Ir (OH) 2Cl4] 3- [Ir (OH) Br5] 3- [Ir (OH) 2Br4] 3- [Ir (O) Cl5] 4- [Ir (O) 2Cl4] 5- [Ir (O) Br5] 4- [Ir ( O) 2Br4] 5- [Ir (OCN) Cl5] 3- [Ir (OCN) Br5] 3- [Ir (thiazole) Cl5] 2- [Ir (thiazole) 2Cl4]-[Ir (thiazole) Br5] 2- [Ir (thiazole) 2Br4]-[Ir (5-methylthiazole) Cl5] 2- [Ir (5-methylthiazole) 2Cl4]-[Ir (5-methylthiazole) Br5] 2- [Ir (5-methylthiazole) -Br2 The subject of this invention is six Any one of six-coordination complexes having Ir as a central metal, wherein all ligands are Cl, Br or I, or six-coordination complexes having Ir as a central metal having at least one ligand other than halogen or cyan It is preferably achieved by using it alone. However, in order to further enhance the effect of the present invention, all six ligands have a six-coordination complex centered on Ir consisting of Cl, Br or I, and Ir having at least one ligand other than halogen or cyan. It is preferable to use together a 6-coordination complex having a central metal. Furthermore, 6-coordination complexes having at least one H 2 O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand consisting of Cl, Br or I as a central metal are 2 Preference is given to using complexes composed of different types of ligands (one from H2 O, OH, O, OCN, thiazole or substituted thiazole and one from Cl, Br or I).

  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.

  These iridium complexes are preferably added in an amount of 1 × 10 −10 mol to 1 × 10 −3 mol per mol of silver during grain formation, and 1 × 10 −8 mol to 1 × 10 −5 mol is preferably added. Most preferred.

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or to 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 iridium complex is 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 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, the particle surface phase is improved by physical ripening with fine particles incorporating the complex in the particles. It is also preferable to improve the quality. 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 the hexacoordinate complex having Ir as the central metal, in which all six ligands are Cl, Br or I, has a silver bromide concentration maximum. It is preferable to contain.

  In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

  A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. The complex containing these cyanide ions as a ligand is preferably added in an amount of 1 × 10 −8 to 1 × 10 −2 mol per mol of silver during grain formation. It is most preferable to add -4 mol. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 −10 mol to 1 × 10 −6 mol, more preferably 1 × 10 −9 mol to 1 × 10 −6 mol, per mol of silver during grain formation. That is.

  The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. As the chemical sensitization method, 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 the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. 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.

  In order to perform gold sensitization on the silver halide emulsion used in the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands are used. be able to. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium thiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

  The silver halide emulsion used in the present invention is preferably gold sensitized with a gold sensitizer having a colloidal gold sulfide or gold complex stability constant log β2 of 21 or more and 35 or less. The method for producing colloidal gold sulfide is described in Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend. Hebt. Seans Acad. Sci. Sect. B 263, 1328, 1966, etc. Various sizes of colloidal gold sulfide can be used, and those having a particle size of 50 nm or less can also be used. The amount added may vary widely depending on the case, but is 5 × 10 −7 to 5 × 10 −3 mol, preferably 5 × 10 −6 to 5 × 10 −4 mol as a gold atom 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.

The gold sensitizer having a gold complex stability constant log β2 of 21 or more and 35 or less will be described below. The measurement of the complex stability constant log β2 of gold is carried out by Comprehensive Coordination Chemistry (Chapter 55, 864, 1987), Encyclopedia of Electrochemistry of the Elements (Encyclopedia of the Elements). Electrochemistry of the Elements, Chapter IV-3, 1975), Journal of the Royal Netherlands Chemical Society, Vol. 101, 164, 198. The measurement method described in the references, etc. is applied, the measurement temperature is 25 ° C., and the pH is diphosphate. Was adjusted to 6.0 with iodine potassium / disodium hydrogen phosphate buffer, ionic strength is obtained by calculating the value of logβ2 from the value of gold potential under conditions of 0.1 M (KBr). In this measurement method, the log β2 value of thiocyanate ion is 20.5, which is described in the literature (Comprehensive Coordination Chemistry, 1987, Chapter 55, page 864, Table 2). A value close to 20 is obtained.
The gold sensitizer having a gold complex stability constant log β2 of 21 to 35 in the present invention is preferably represented by the following general formula (I).

  General formula (I) {(L1) x (Au) y (L2) z · Qq} p In general formula (I), L1 and L2 each independently have a value of log β2 between 21 and 35 Represents a compound. Preferably, it is a compound contained between 22 and 31, more preferably a compound contained between 24 and 28.

  L1 and L2 are, for example, compounds containing at least one labile sulfur group capable of reacting with silver halide to produce silver sulfide, hydantoin compounds, thioether compounds, mesoionic compounds, -SR ', heterocyclic compounds Represents a phosphine compound, an amino acid derivative, a sugar derivative, and a thiocyano group, which may be the same as or different from each other. Here, R ′ represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a thiocarbamoyl group, or a sulfonyl group. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q represents 0 including a decimal number. Represents a value of ~ 1. However, neither x nor z is 0.

The compound represented by the general formula (I) is preferably a compound in which L1 and L2 contain at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, a hydantoin compound, a thioether Represents a compound, a mesoionic compound, -SR ', a heterocyclic compound, or a phosphine compound, and x, y, and z each represent 1.
More preferably as a compound represented by the general formula (I), a compound in which L1 and L2 contain at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, a mesoionic compound, Or -SR 'and x, y, z, and p each represent 1.
Hereinafter, the gold compound represented by the general formula (I) will be described in more detail. In general formula (I), compounds having unstable sulfur groups that can react with silver halides represented by L1 and L2 to form silver sulfide include thioketones (for example, thioureas, thioamides). Or rhodanines), thiophosphates, thiosulfates.
A compound containing at least one unstable sulfur group capable of reacting with silver halide to produce silver sulfide preferably represents thioketones (preferably thioureas, thioamides, etc.) and thiosulfuric acids. .

  Next, in the general formula (I), examples of the hydantoin compound represented by L1 and L2 include unsubstituted hydantoin, N-methylhydantoin, etc., and the thioether compound includes 1 to 8 thio groups. A linear or branched alkylene group (for example, ethylene, triethylene, etc.) which is substituted or unsubstituted, or a chain or cyclic thioether linked by a phenylene group (for example, bishydroxyethyl thioether, 3 , 6-dithia-1,8-octanediol, 1,4,8,11-tetrathiacyclotetradecane, etc.), and mesoionic compounds include mesoionic-3-mercapto-1,2,4-triazole. (For example, mesoionic-1,4,5-trimethyl-3-mercapto-1,2,4-triazole etc.) etc. And the like.

  Next, in the general formula (I), when L 1 and L 2 represent —SR ′, the aliphatic hydrocarbon group represented by R ′ is a substituted or unsubstituted linear or branched group having 1 to 30 carbon atoms. Alkyl groups (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 1,5-dimethylhexyl) , N-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2,3-dihydroxypropyl, carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl, ethoxy Ethoxyethyl, n-hexyloxypropyl, etc.), substituted 3 to 18 carbon atoms Or an unsubstituted cyclic alkyl group (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, cyclododecyl, etc.), an alkenyl group having 2 to 16 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl, etc.) , An alkynyl group having 2 to 10 carbon atoms (for example, propargyl, 3-pentynyl and the like), an aralkyl group having 6 to 16 carbon atoms (for example, benzyl and the like) and the like, and an aryl group having 6 to 20 carbon atoms. Substituted or unsubstituted phenyl group and naphthyl group (for example, unsubstituted phenyl, unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl, etc.) Examples of the ring group include a substituted or unsubstituted nitrogen-containing hetero 5-membered ring (for example, imida Zolyl, 1,2,4-triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.), substituted or unsubstituted nitrogen-containing hetero 6-membered ring (for example, pyridyl, piperidyl, 1,3,5-triazino, 4, 6-dimercapto-1,3,5-triazino and the like), furyl group, thienyl group and the like. Examples of the acyl group include acetyl and benzoyl. Examples of the carbamoyl group include dimethylcarbamoyl and the like. Examples of the thiocarbamoyl group include diethylthiocarbamoyl, and the sulfonyl group includes a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms (for example, methanesulfonyl, ethanesulfonyl, etc.), and 6 to 16 carbon atoms. Substituted or unsubstituted phenylsulfo Le group (e.g., phenylsulfonyl, etc.).

  In addition, as -SR ′ represented by L 1 and L 2, R ′ is preferably an aryl group or a heterocyclic group, more preferably a heterocyclic group, and further preferably a 5-membered or 6-membered nitrogen-containing heterocyclic ring. Most preferably a nitrogen-containing heterocyclic group substituted with a water-soluble group (for example, sulfo, carboxy, hydroxy, amino, etc.).

  In the general formula (I), the heterocyclic compounds represented by L1 and L2 include substituted or unsubstituted nitrogen-containing hetero 5-membered rings (for example, pyrroles, imidazoles, pyrazoles, 1,2,3- Triazoles, 1,2,4-triazoles, tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, Pyrazolines, hydantoins, etc.) and heterocycles containing the 5-membered ring (indoles, isoindoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraaza Indene, benzothiazole, indoline, etc.), substituted or Substituted nitrogen-containing hetero 6-membered rings (for example, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines, piperidines, piperazines, morpholines, etc.) and heteros containing the 6-membered rings Rings (eg, quinolines, isoquinolines, phthalazines, naphthyridines, quinoxalines, quinazolines, pteridines, phenaziridines, acridines, phenanthrolines, phenazines), substituted or unsubstituted furans, substituted or Examples thereof include unsubstituted thiophenes and benzothiazoliums.

The heterocyclic compound represented by L1 and L2 is preferably an unsaturated nitrogen-containing hetero 5-membered or 6-membered ring or a heterocyclic ring containing it, such as pyrroles, imidazoles, and pyrazoles. 1,2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, Benzothiazoles, pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines and the like, and further, heterocyclic compounds known as antifoggants in the art (for example, , Indazoles, benzimidazoles, benzotriazole , Tetraazaindene, etc.) are preferable.
In the general formula (I), the phosphine compound represented by L1 and L2 includes an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heterocyclic group (for example, pyridyl etc.), substituted Or an unsubstituted amino group (for example, dimethylamino and the like) and / or an alkyloxy group (for example, methyloxy, ethyloxy and the like) substituted phosphines, preferably an alkyl group having 1 to 10 carbon atoms, Alternatively, phosphines substituted with an aryl group having 6 to 12 carbon atoms (for example, triphenylphosphine, triethylphosphine, etc.) and the like can be mentioned.

Furthermore, the above mesoionic compounds represented by L1 and L2, -SR ', and heterocyclic compounds include unstable sulfur groups (for example, thioureido groups) that can react with silver halide to form silver sulfide. Etc.) are preferably substituted.
The compounds represented by L1 and L2 in the general formula (I) may further have as many substituents as possible. Examples of the substituents include halogen atoms (for example, fluorine atoms, chlorines). Atoms, bromine atoms, etc.), aliphatic hydrocarbon groups (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl etc.), alkynyl groups (eg propargyl, 3-pentynyl etc.), aralkyl groups (eg benzyl, phenethyl etc.), aryl groups (eg phenyl, naphthyl, 4-methylphenyl etc.), heterocyclic groups ( For example, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl, etc.), alkyloxy groups (for example, methoxy, ethoxy, Xyl, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy, etc.), aryloxy groups (eg, phenoxy, 2-naphthyloxy, etc.), amino groups (eg, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutylamino) , Ethylamino, dibenzylamino, anilino etc.), acylamino group (eg acetylamino, benzoylamino etc.), ureido group (eg unsubstituted ureido, N-methylureido, N-phenylureido etc.), thioureido group (eg , Unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, etc.), selenoureido group (eg, unsubstituted selenoureide etc.), phosphine selenide group (diphenylphosphine selenide etc.), tellurolide group (eg, unsubstituted telluride) Ureido etc.), urethane group (eg methoxycarbonylamino, phenoxycarbonylamino etc.), sulfonamide group (eg methylsulfonamide, phenylsulfonamide etc.), sulfamoyl group (eg unsubstituted sulfamoyl group, N, N-dimethyl) Sulfamoyl, N-phenylsulfamoyl, etc.), carbamoyl groups (eg, unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, etc.), sulfonyl groups (eg, methanesulfonyl, p-toluenesulfonyl, etc.) , Sulfinyl groups (eg methylsulfinyl, phenylsulfinyl etc.), alkyloxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl groups (eg phenoxycarbonyl etc.), Group (for example, acetyl, benzoyl, formyl, pivaloyl, etc.), acyloxy group (for example, acetoxy, benzoyloxy, etc.), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide, etc.), alkylthio group (for example, Methylthio, ethylthio, etc.), arylthio groups (eg, phenylthio, etc.), cyano groups, sulfo groups, thiosulfonic acid groups, sulfinic acid groups, carboxy groups, hydroxy groups, mercapto groups, phosphono groups, nitro groups, sulfino groups, ammonio groups ( For example, trimethylammonio etc.), phosphonio group, hydrazino group, thiazolino group, silyloxy group (eg t-butyldimethylsilyloxy, t-butyldiphenylsilyloxy) and the like. Moreover, when there are two or more substituents, they may be the same or different.

  Next, Q and q in the general formula (I) will be described. In the general formula (I), examples of the counter anion represented by Q include halogenium ions (for example, F-, Cl-, Br-, I-), tetrafluoroborate ions (BF4-), hexafluorophosphate ions ( PF6-), sulfate ion (SO42-), arylsulfonate ion (for example, p-toluenesulfonate ion, naphthalene-2,5-disulfonate ion, etc.), carboxy ion (for example, acetate ion, trifluoroacetate ion, oxalate ion) The counter cation represented by Q includes alkali metal ions (for example, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, etc.), alkaline earth metal ions ( For example, magnesium ion, calcium ion, etc.), substituted or non-placed And ammonium ions (eg, unsubstituted ammonium ion, triethylammonium, tetramethylammonium, etc.), substituted or unsubstituted pyridinium ions (eg, unsubstituted pyridinium ion, 4-phenylpyridinium ion, etc.), and protons. . Further, q is the number of Q for neutralizing the charge of the compound, and represents a value from 0 to 1, and the value may be a decimal number.

The counter anion represented by Q is preferably a halogenium ion (for example, Cl-, Br-), tetrafluoroborate ion, hexafluorophosphate ion, or sulfate ion, and the counter cation represented by Q is preferably an alkali. It is a metal ion (for example, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), a substituted or unsubstituted ammonium ion (for example, unsubstituted ammonium ion, triethylammonium, tetramethylammonium, etc.), or a proton.
Specific examples (L-1 to L-17) of the compound represented by L1 or L2 are shown below, but the present invention is not limited thereto. The numerical value in parentheses indicates the log β2 value.

The compound represented by the general formula (I) can be obtained by a known method such as Inorganic and Nuclear Chemistry Letters (INORG.NUCL.CHEM.LETTERSVOL.10, 641, 1974), Transition Metal Chemistry (TransitionMet. Chem. 1, 248, 1976), Acta Crystallographica (Acta. Cryst. B32, 3321, 1976), JP-A-8-69075, JP-B-45-8831, Europe The compound can be synthesized with reference to Japanese Patent No. 915371A1, JP-A-6-11788, JP-A-6-501789, JP-A-4-267249, JP-A-9-118865, and the like.
Next, although the specific example (S-1 to S-19) of a compound represented by general formula (I) is shown, this invention is not limited to these.

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature (preferably 40 ° C. or higher) for a predetermined time. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 −7 mol or more and 1 × 10 −4 mol or less per mol of silver halide.

  In the present invention, as a gold sensitizer, in addition to the above-mentioned compounds, commonly used gold compounds (for example, chloroaurate, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodoaurate, tetracyanoauric) Acid, ammonium aurothiocyanate, pyridyltrichlorogold, etc.) can be used in combination.

The silver halide emulsion used in the present invention can be used in combination with other chemical sensitization in addition to gold sensitization. Examples of chemical sensitization methods that can be used in combination include sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals other than gold, or reduction sensitization. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.
To the silver halide emulsion used in the present invention, various compounds or precursors thereof are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. can do. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Furthermore, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP 0447647 is also preferably used.

  In the present invention, in order to enhance the storage stability of the silver halide emulsion, both ends are adjacent to the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094. Cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the specification of the present application), particularly Sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4 -Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid Acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 556,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and is incorporated as part of the present specification), Japanese Patent Application Laid-Open No. 11-102045. The water-soluble reducing agents represented by the general formulas (I) to (III) in the publication are also preferably used in the present invention.

  The silver halide emulsion used in the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.

The amount of these spectral sensitizing dyes to be added varies widely depending on the case, and is preferably in the range of 0.5.times.10@-6 mol to 1.0.times.10@-2 mol per mol of silver halide. More preferably, it is in the range of 1.0 × 10 −6 mol to 5.0 × 10 −3 mol.
[Silver halide color photographic light-sensitive material] Next, the silver halide color photographic light-sensitive material of the present invention will be described. As described above, the silver halide color photographic light-sensitive material of the present invention comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red light sensitive material on a support. A silver halide emulsion layer. The yellow-colored blue-sensitive silver halide emulsion layer is a yellow-colored layer containing a yellow dye-forming coupler, the magenta-colored green-sensitive silver halide emulsion layer is a magenta-colored layer containing a magenta dye-forming coupler, and a cyan-colored red light-sensitive layer The silver halide emulsion layer functions as a cyan color forming layer containing the cyan dye-forming coupler. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region, and red region). Have.

  Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention. For example, as the photographic support, a transmissive support or a reflective support can be used. As the transmissive support, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), NDCA, terephthalic acid and EG are used. A polyester provided with an information recording layer such as a magnetic layer is preferably used. In the present invention, a reflective support (also referred to as a reflective support) is preferable, and the reflective support is particularly laminated with a plurality of polyethylene layers or polyester layers, and such a water-resistant resin layer (laminate layer). A reflective support containing a white pigment such as titanium oxide in at least one layer is preferred.

  In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg, polypropylene, polyethylene) and is on a paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single layer of polyolefin positioned between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, and more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

  In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support in the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are disclosed in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, and JP-A-11-65024. Examples are described in EP0880065 and EP0880066.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent brighteners are more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m2. The mixing ratio in the case of mixing with a water-resistant resin is preferably 0.0005 to 3 mass%, more preferably 0.001 to 0.5 mass%, based on the resin.
The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular or second-type diffuse reflective metal surface.
In addition, as a support used in the light-sensitive material of the present invention, a support provided with a white polyester support or a layer containing a white pigment on a support having a silver halide emulsion layer for display is used. May be. In order to further improve the sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coating side or the back surface of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with either reflected light or transmitted light.

  In the light-sensitive material of the present invention, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is applied to a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Among them, oxonol dyes are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or divalent to tetravalent alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. ) Etc. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated.

  In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of EP 0337490 A2 is carried out on the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3 from the upper right column to page 8, and the dyes described in JP-A-3-7931, page 3 from upper right column to page 11, lower left column are solid. A method of incorporating a hydrophilic colloid layer in the form of a fine particle dispersion, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-239544 For example, a method using colloidal silver as described in Japanese Patent Publication. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 2-308244, pages 4 to 13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show preparation methods for colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  The photosensitive material of the present invention is used for color negative film, color positive film, color reversal film, color reversal photographic paper, color photographic paper display photosensitive material, digital color proof, movie color positive, movie color negative, etc. Materials, digital color proofs, color positives for movies, color reversal photographic papers, and color photographic papers are preferred, and particularly preferred as color photographic papers. As described above, the color photographic paper has at least one yellow-colored blue-sensitive silver halide emulsion layer, magenta-colored green-sensitive silver halide emulsion layer, and cyan-colored red-sensitive silver halide emulsion layer. In general, these silver halide emulsion layers are arranged in the order from the support to the yellow-colored blue-sensitive silver halide emulsion layer, the magenta-colored green-sensitive silver halide emulsion layer, and the cyan-colored red-sensitive halogen halide. It is a silver halide emulsion layer.

  However, a different layer structure may be used. The blue-sensitive silver halide emulsion layer may be disposed at any position on the support. However, when the blue-sensitive silver halide emulsion layer contains tabular grains of green halide, It is preferably coated at a position farther from the support than at least one of the silver halide emulsion layer or the red-sensitive silver halide emulsion layer. From the viewpoint of promoting color development, desilvering, and reducing residual color by sensitizing dye, the blue-sensitive silver halide emulsion layer is coated at the position farthest from the support than the other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the red-sensitive silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the red-sensitive silver halide emulsion layer is preferred. Is preferably the lowermost layer. Further, each color developing layer of yellow, magenta and cyan may be composed of two layers or three layers. For example, couplers containing no silver halide emulsion as described in JP-A-4-75055, JP-A-9-1114035, JP-A-10-246940, US Pat. No. 5,576,159, etc. It is also preferable to provide a layer adjacent to the silver halide emulsion layer to form a color developing layer.

As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly described in European Patent EP0,355,660A2. Are preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433. No. 2-854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, EP-A-0520457A2, and the like. A silver halide color photographic light-sensitive material and a processing method thereof are also preferable.
In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), gelatin type, layer structure of the photosensitive material, and coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applied.

Other examples of cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful. In the present invention, compounds represented by the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.

As a cyan dye-forming coupler that can be used in the present invention (sometimes simply referred to as “cyan coupler”), a pyrrolotriazole-based coupler is preferably used, and the general formula (I) or (II) described in JP-A-5-313324 is used. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole type cyan couplers described in European Patents EP0488248 and EP0491197A1, and 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716. US Pat. Nos. 4,873,183 and 4,916,051, pyrazoloazole type cyan couplers having an electron-attracting group and a hydrogen-bonding group at the 6-position, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-311360, and JP-A-8-339060 are also preferable.
In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (particularly, coupler (42) listed as a specific example) A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) (Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 0456226A1, and pyrroloimidazole type cyan couplers described in EP 0484909 are used. You can also.
Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present application as they are, and are preferably incorporated as part of the specification of the present application.

  Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is the 2, 3, or 6 position of the pyrazolotriazole ring among them in terms of hue, image stability, color developability, etc. A pyrazolotriazole coupler directly connected to a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, as described in JP-A-61-147254 Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group, European Patent No. 226,849A, Use of pyrazoloazole couplers having a 6-position alkoxy or aryloxy group as described in the 294,785A Pat are preferred. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent are directly applied to the present application. As part of the specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.

  Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in European Patent EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Patent Publication Nos. 935870A1, 953871A1, and 957,72A1 Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide type couplers described in U.S. Pat. Nos. 5,953,873, 953874, 1,953875A1, etc. Described in the specification of 5,118,599 Acylacetamide yellow couplers having a a dioxane structure is preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used alone or in combination.

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

  In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, US Pat. No. 4,923,787, etc. White couplers described in Japanese Patent No. 249637, Japanese Patent Application Laid-Open No. 10-282615, German Patent No. 19629142A1, and the like can be used. In particular, in the case of increasing the pH of the developer to speed up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 180686846A1 And redox compounds described in French Patent No. 2760460A1 are also preferable.

  In the present invention, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. The compounds described in the specification of 19739797A, European Patent No. 711804A and JP-A-8-501291 can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m 2 or less, more preferably 10 mg / m 2 or less, and most preferably 5 mg / m 2 or less.
In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

  In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 −5 to 1 g / m 2, preferably 1 × 10 −4 to 1 × 10 −1 g. / M @ 2, more preferably 1.times.10@-3 to 1.times.10@-2 g / m @ 2.

  The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed. The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

  When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

  The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

  The photosensitive material of the present invention is preferably imagewise exposed with coherent light of a blue laser having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.

  Here, as a laser light source, specifically, a blue semiconductor laser with a wavelength of 430 to 450 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength: about 940 nm) About 470 nm of blue laser and semiconductor laser (oscillation wavelength: about 1060 nm) extracted from a LiNbO3 SHG crystal having a waveguide-like inversion domain structure and an LiNbO3 SHG crystal having a waveguide-like inversion domain structure A green laser having a wavelength of about 530 nm, a red semiconductor laser having a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG), and the like are preferably used.

  When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In an SHG light source obtained by combining a solid-state laser using a semiconductor laser as an excitation light source or a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 −4 seconds or less, more preferably 10 −6 seconds or less.

  The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnosis system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in Japanese Patent Application No. 10-159187.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
When the light-sensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility. In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, the yellow microdot pattern may be pre-exposed in advance and copy control may be performed before image information is added. .
In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

  The photosensitive material of the present invention is preferably applied as a photosensitive material having rapid processing suitability. When rapid processing is performed, the color development time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. Similarly, the bleach-fixing time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. The washing or stabilizing time is preferably 60 seconds or shorter, more preferably 40 seconds or shorter and 6 seconds or longer.

  The color development time is the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

  In the light-sensitive material of the present invention, the color development time is particularly preferably 20 seconds or less (preferably 6 to 20 seconds, more preferably 6 to 15 seconds). Here, in the present invention, color development processing with a color development time of 20 seconds or less means that the color development time described above is 20 seconds or less (not the entire time of color development processing).

  The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small. In the activator method, as a developing agent or a precursor thereof incorporated in the photosensitive material, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, and JP-A-9-212814. The hydrazine type compounds described in JP-A-9-160193 are preferred.

  Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used.

  In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.

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

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Example 1]
(Preparation of emulsion B-1) 1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were vigorously stirred. Simultaneously added and mixed at 66 ° C. From 80% to 90% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 2 mol% per mole of finished silver halide. From the time point when the addition of silver nitrate was 80% to 90%, the K4 [Ru (CN) 6] aqueous solution was added in such an amount that the amount of Ru was 3 × 10 −5 mol per mol of the finished silver halide. From the point of 83% addition of silver nitrate to the point of 88%, an aqueous solution of K2 [IrCl6] was added so that the amount of Ir per mol of the finished silver halide was 3 × 10 −8 mol. When 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.2 mol% per mol of the finished silver halide. From 92% to 98% addition of silver nitrate, K2 [Ir (5-methylthiazole) Cl5] aqueous solution was added in an amount such that the amount of Ir per mol of the finished silver halide was 1 × 10 −6 mol. . After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grain was a cubic silver iodobromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. This emulsion was dissolved at 40 ° C., 2 × 10 −5 mol of sodium thiosulfonate was added per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S— 2) was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., sensitizing dye A was 2 × 10 −4 mol per mol of silver halide, sensitizing dye B was 1 × 10 −4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole 2 × 10 −4 mol per mol of silver halide, 1 × (5-methylureidophenyl) -5-mercaptotetrazole 2 × 10 −4 mol per mol of silver halide, potassium bromide 1 mol of silver halide 2 × 10 −3 moles were added per mole. The emulsion thus obtained was designated as Emulsion B-1.

(Preparation of emulsion B-2) 1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were vigorously stirred. Simultaneously added and mixed at 55 ° C. From 80% to 90% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 2 mol% per mole of finished silver halide. From the time point when the addition of silver nitrate was 80% to 90%, the K4 [Ru (CN) 6] aqueous solution was added in such an amount that the amount of Ru was 3 × 10 −5 mol per mol of the finished silver halide. From the time when the addition of silver nitrate was 83% to the time of 88%, the K2 [IrCl6] aqueous solution was added in an amount such that the amount of Ir per mol of the finished silver halide was 5 × 10 −8 mol. When 90% of the addition of silver nitrate had been completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.3 mol% per mol of the finished silver halide. From the time when the addition of silver nitrate is 92% to the time when it is 98%, the amount of Ir is 1.7 × 10 −6 mol per mol of the finished silver halide in the K 2 [Ir (5-methylthiazole) Cl 5] aqueous solution. Added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride emulsions having a sphere equivalent diameter of 0.55 μm and a coefficient of variation of 11%. This emulsion was dissolved at 40 ° C., 2 × 10 −5 mol of sodium thiosulfonate was added per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S— 2) was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., sensitizing dye A was 2.7 × 10 −4 mol per mol of silver halide, and sensitizing dye B was 1.4 × 10 −4 mol per mol of silver halide, 1-phenyl- 2.7 × 10 −4 mol of 5-mercaptotetrazole per mol of silver halide, 2.7 × 10 −4 mol of 1- (5-methylureidophenyl) -5-mercaptotetrazole per mol of silver halide, Potassium bromide was added at 2.7 × 10 −3 mole per mole of silver halide. The emulsion thus obtained was designated as Emulsion B-2.

(Preparation of Emulsion G-1) 1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, while vigorously stirring an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride. Simultaneously added and mixed at 50 ° C. From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 3 mol% per mole of finished silver halide. From the time point when the addition of silver nitrate was 80% to 90%, the K4 [Ru (CN) 6] aqueous solution was added in such an amount that the amount of Ru was 3 × 10 −5 mol per mol of the finished silver halide. From the time when the addition of silver nitrate was 83% to the time of 88%, the K2 [IrCl6] aqueous solution was added in an amount such that the amount of Ir per mol of the finished silver halide was 5 × 10 −8 mol. Further, when 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added with vigorous mixing in such an amount that the amount of I was 0.05 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, an aqueous K2 [Ir (5-methylthiazole) Cl5] solution was added in an amount of 5 × 10 −7 mol per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to 98%, an aqueous solution of K2 [Ir (H2O) Cl5] was added so that the amount of Ir was 5 × 10 -7 mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver chloride emulsions having a sphere equivalent diameter of 0.45 μm and a coefficient of variation of 10%. This emulsion was dissolved at 40 ° C., 2 × 10 −5 mol of sodium thiosulfonate was added per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S— 2) was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., the sensitizing dye D was 4.7 × 10 −4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole was 1.6 × 10 −4 mol per mol of silver halide, 1- (5-Methylureidophenyl) -5-mercaptotetrazole was added at 6.2 × 10 −4 mol per mol of silver halide and potassium bromide was added at 5.4 × 10 −3 mol per mol of silver halide. . The emulsion thus obtained was designated as Emulsion G-1.

(Preparation of Emulsion G-2) 1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, while vigorously stirring an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride. Simultaneously added and mixed at 45 ° C. From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 4 mol% per mole of finished silver halide. From the time point when the addition of silver nitrate was 80% to 90%, the K4 [Ru (CN) 6] aqueous solution was added in such an amount that the amount of Ru was 3 × 10 −5 mol per mol of the finished silver halide. From the time when the addition of silver nitrate was 83% to the time of 88%, the K2 [IrCl6] aqueous solution was added in an amount such that the amount of Ir per mol of the finished silver halide was 5 × 10 −8 mol. Further, when 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.15 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, an aqueous K2 [Ir (5-methylthiazole) Cl5] solution was added in an amount of 5 × 10 −7 mol per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to 98%, an aqueous solution of K2 [Ir (H2O) Cl5] was added so that the amount of Ir was 5 × 10 -7 mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver chloride emulsions having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10%. This emulsion was dissolved at 40 ° C., 2 × 10 −5 mol of sodium thiosulfonate was added per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S— 2) was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., sensitizing dye D was 6 × 10 −4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole was 2 × 10 −4 mol per mol of silver halide, 1- (5 -Methylureidophenyl) -5-mercaptotetrazole was added at 8 * 10 <-4> mol per mole of silver halide and potassium bromide was added at 7 * 10 <-3> mol per mole of silver halide. The emulsion thus obtained was designated as Emulsion G-2.

  (Preparation of emulsion R-1) 1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were vigorously stirred. Simultaneously added and mixed at 50 ° C. From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 3 mol% per mole of finished silver halide. From the time point when the addition of silver nitrate was 80% to 90%, the K4 [Ru (CN) 6] aqueous solution was added in such an amount that the amount of Ru was 3 × 10 −5 mol per mol of the finished silver halide. From the time when the addition of silver nitrate was 83% to the time of 88%, the K2 [IrCl6] aqueous solution was added in an amount such that the amount of Ir per mol of the finished silver halide was 5 × 10 −8 mol. When 90% of the addition of silver nitrate had been completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.05 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, an aqueous K2 [Ir (5-methylthiazole) Cl5] solution was added in an amount of 5 × 10 −7 mol per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to 98%, an aqueous solution of K2 [Ir (H2O) Cl5] was added so that the amount of Ir was 5 × 10 -7 mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride emulsions having a sphere equivalent diameter of 0.45 μm and a coefficient of variation of 10%. This emulsion was dissolved at 40 ° C., 2 × 10 −5 mol of sodium thiosulfonate was added per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S— 2) was used for aging at 60 ° C. After cooling to 40 ° C., the sensitizing dye H is 1.6 × 10 −4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole is 1.6 × 10 −4 mol per mol of silver halide, 1- (5-Methylureidophenyl) -5-mercaptotetrazole 6.2 × 10 −4 mol per mol of silver halide, Compound I 7.7 × 10 −4 mol per mol of silver halide, bromide Potassium was added at 5.4.times.10@-3 mol per mol of silver halide. The emulsion thus obtained was designated as Emulsion R-1.

(Preparation of emulsion R-2) 1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were vigorously stirred. Simultaneously added and mixed at 45 ° C. From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 4 mol% per mole of finished silver halide. From the time point when the addition of silver nitrate was 80% to 90%, the K4 [Ru (CN) 6] aqueous solution was added in such an amount that the amount of Ru was 3 × 10 −5 mol per mol of the finished silver halide. From the time when the addition of silver nitrate was 83% to the time of 88%, the K2 [IrCl6] aqueous solution was added in an amount such that the amount of Ir per mol of the finished silver halide was 5 × 10 −8 mol. When 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.15 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, an aqueous K2 [Ir (5-methylthiazole) Cl5] solution was added in an amount of 5 × 10 −7 mol per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to the time when it was 98%, an aqueous solution of K2 [Ir (H2O) Cl5] was added so that the amount of Ir was 5 × 10 -7 mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride emulsions having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10%. This emulsion was dissolved at 40 ° C., 2 × 10 −5 mol of sodium thiosulfonate was added per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S— 2) was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., the sensitizing dye H was 2 × 10 −4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole was 2 × 10 −4 mol per mol of silver halide, 1- (5 -Methylureidophenyl) -5-mercaptotetrazole 8 × 10 −4 mole per mole of silver halide, Compound I 1 × 10 −3 mole per mole of silver halide, and potassium bromide per mole of silver halide 7 × 10 −3 mol was added. The emulsion thus obtained was designated as Emulsion R-2.

  (Preparation of sample) After applying corona discharge treatment to the surface of the support obtained by coating both sides of the paper with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided, and the first to second layers Seven layers of photographic constituent layers were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

-First layer coating solution preparation-57 g of yellow coupler (ExY), 7 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), 7 g of color image stabilizer (Cpd-3), color image 2 g of stabilizer (Cpd-8) was dissolved in 21 g of solvent (Solv-1) and 80 ml of ethyl acetate, and this liquid was stirred and emulsified in 220 g of a 23.5 mass% gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate. Emulsified and dispersed with (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion B-1 were mixed and dissolved, and a first layer coating solution was prepared so as to have the composition described later. The emulsion coating amount indicates the silver coating amount.
-Preparation of second-layer to seventh-layer coating solution-Second- to seventh-layer coating solutions were prepared in the same manner as the first-layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. In addition, Ab-1, Ab-2, Ab-3, and Ab-4 are added to each layer so that the total amount is 15.0 mg / m2, 60.0 mg / m2, 5.0 mg / m2, and 10.0 mg / m2, respectively. Added to.

Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0.times.10@-3 mol and 5.9.times.10@-4 mol per mol of silver halide, respectively. . Furthermore, 1-phenyl-5-mercaptotetrazole was added to the second layer, the fourth layer, and the sixth layer so that the amounts were 0.2 mg / m @ 2, 0.2 mg / m @ 2 and 0.6 mg / m @ 2, respectively. Copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer at 0.05 g / m 2. Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer and the sixth layer so as to be 6 mg / m 2, 6 mg / m 2 and 18 mg / m 2, respectively. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m @ 2). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin laminated paper [White pigment (TiO2; content: 16% by mass, ZnO; content: 4% by mass) and fluorescent whitening agent (4,4′-bis (5-methyl) on the polyethylene resin on the first layer side] Benzoxazolyl) stilbene, containing 0.03% by mass), including a bluish dye (ultraviolet)]
First layer (blue sensitive emulsion layer)
Emulsion B-1 0.26 Gelatin 1.25 Yellow coupler (ExY-1) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer ( Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21
Second layer (color mixing prevention layer)
Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0. 01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.15 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) ) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0 .01 Color Image Stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20
Fourth layer (color mixing prevention layer)
Gelatin 0.71 Color mixing prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0. 007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16
5th layer (red-sensitive emulsion layer)
Emulsion R-1 0.13 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd- 6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0. 07 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05
Sixth layer (UV absorbing layer)
Gelatin 0.46 Ultraviolet absorber (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25
Seventh layer (protective layer)
Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

The sample obtained as described above was designated as Sample 101. Samples 101 to 104 were prepared in the same manner as Sample 101 except that the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer were replaced as shown in Table 2.
In addition, the sample 101 was prepared by changing the photographic composition layer as described below to make it thinner.
First layer (blue sensitive emulsion layer)
Emulsion B-1 0.14 Gelatin 0.75 Yellow coupler (ExY-2) 0.34 Color image stabilizer (Cpd-1) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer ( Cpd-3) 0.04 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-1) 0.13
Second layer (color mixing prevention layer)
Gelatin 0.60 Color mixing inhibitor (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 Ultraviolet absorber (UV-C) 0.05 Solvent (Solv-5) 0.11
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.14 Gelatin 0.73 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.05 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-7) ) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0 .0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0.06
Fourth layer (color mixing prevention layer)
Gelatin 0.48 Color mixing prevention layer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 Ultraviolet absorber (UV-C) 0.04 Solvent (Solv-5) 0.09
5th layer (red-sensitive emulsion layer)
Emulsion R-1 0.12 Gelatin 0.59 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd- 9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 0.04 Ultraviolet absorber (UV-7) 0.02 Solvent (Solv-5) 0.09
Sixth layer (UV absorbing layer)
Gelatin 0.32 Ultraviolet absorber (UV-C) 0.42 Solvent (Solv-7) 0.08
Seventh layer (protective layer)
Gelatin 0.70 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

The sample obtained as described above was designated as Sample 105. Samples 105 were prepared in the same manner as samples 105 except that the emulsions of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer were changed as shown in Table 2.

(Evaluation) In order to examine the photographic characteristics of these samples, the following experiment was conducted. Each coated sample was subjected to 10-6 seconds high illuminance gradation exposure for gray color sensitometry using a high illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.).
For each of the exposed samples, the color development processing was performed ultra-rapid processing according to the following development processing.

  [Processing] The photosensitive material sample was processed into a 127 mm wide roll, and the experimental processing apparatus was modified from the Fuji Photo Film minilab printer processor PP350 so that the processing time and processing temperature could be changed. Samples were imagewise exposed from an average density negative film and subjected to continuous processing (running test) until the volume of the color developer replenisher used in the following processing steps was 0.5 times the color developer tank volume.

  Processing Step Temperature Time Replenishment amount * Color development 45.0 ° C 15 seconds 45mL Bleach fixing 40.0 ° C 15 seconds 35mL Rinse (1) 40.0 ° C 8 seconds-Rinse (2) 40.0 ° C 8 seconds-Rinse (3 ) * 40.0 ° C. 8 seconds-Rinse (4) ** 38.0 ° C. 8 seconds 121 mL Drying 80.0 ° C. 15 seconds (Note) * Replenishment amount per 1 m 2 of photosensitive material ** Fuji Photo Film Co., Ltd. The phosphorus screening system RC50D is attached to the rinse (3), and the rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse, and the concentrate is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a four-tank countercurrent system from (1) to (4).

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
Water 800 mL 600 mL fluorescent brightening agent (FL-1) 5.0 g 8.5 g triisopropanolamine 8.8 g 8.8 gp-sodium toluenesulfonate 20.0 g 20.0 g ethylenediaminetetraacetic acid 4.0 g 4.0 g sodium sulfite 0 .10 g 0.50 g Potassium chloride 10.0 g -4,5-Dihydroxybenzene-1,3-disulfonate sodium 0.50 g 0.50 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14 0.5 g 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate 10.0 g 22.0 g potassium carbonate 26.3 g 26.3 g In addition, total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6
[Bleaching Fixer] [Tank Solution] [Replenisher] Water 800 mL 800 mL Ammonium Thiosulfate (750 g / L)
107 mL 214 mL Succinic acid 29.5 g 59.0 g Ethylenediaminetetraacetic acid iron (III) ammonium 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 17.5 g 35.0 g Imidazole 14.6 g 29. 2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Water added to total volume 1000 mL 1000 mL pH (adjusted with nitric acid and aqueous ammonia) 6.00 6.00
[Rinse solution] [Tank solution] [Replenisher solution] Chlorinated isocyanurate sodium 0.02 g 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6.5

The yellow color density of each sample after processing was measured, and a characteristic curve of 10-6 seconds high-illuminance exposure was obtained. The gradation (γ) was obtained from the slope of a straight line connecting points of density 1.5 and density 2.0. Higher values are preferable for higher contrast. The sensitivity fluctuation (ΔS) when the development time fluctuates is the difference between the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density when the color development time is 20 seconds and 15 seconds. Was expressed logarithmically. A smaller value is more stable and preferable. These results are shown in Table 3.

As is apparent from the results in Table 3, it is recognized that the samples 107 and 108 of the present invention have a high gradation in the yellow coloring layer, a small sensitivity fluctuation when the development time is changed, and excellent rapid processing properties. It was.

Example 2 Using the sample of Example 1, an image was formed by laser scanning exposure. As a laser light source, a blue semiconductor laser having a wavelength of about 440 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength: about 1060 nm) is used as a waveguide-like inversion domain. A green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG) taken out by converting the wavelength using a LiNbO3 SHG crystal having a structure were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 −7 seconds. This exposure method gave gray exposure for gray color sensitometry.
After the exposure, the color development processing was performed. The yellow color density of each sample after treatment was measured to obtain a characteristic curve for laser exposure. The gradation (γ) was obtained from the slope of a straight line connecting points of density 1.5 and density 2.0. Higher values are preferable for higher contrast. The sensitivity fluctuation (ΔS) when the development time fluctuates is the difference between the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density when the color development time is 20 seconds and 15 seconds. Was expressed logarithmically. A smaller value is more stable and preferable. These results are also shown in Table 3.
In the samples 107 and 108 of the present invention, the yellow coloring layer showed a high gradation, and the sensitivity fluctuation was small when the development time was changed. In addition, this effect was greater than the result of the high illumination exposure in Example 1, and it was found that this was suitable for image formation using laser scanning exposure.

  From these Examples and Comparative Examples, it can be seen that the photosensitive material of the present invention can obtain a particularly high gradation in digital exposure such as laser scanning exposure, and can obtain stable performance even when the processing factors fluctuate.

  Since the present embodiment is configured as described above, an exposure apparatus having excellent beam quality, a sufficient extinction ratio, and matching the characteristics of the silver salt photosensitive material can be obtained.

1 is a perspective view of an exposure apparatus according to Embodiment 1. FIG. It is a side view of the exposure apparatus which concerns on this Embodiment 1. FIG. It is a figure showing the effect of the 1st slit concerning this Embodiment 1. It is a figure showing the effect of the 1st slit concerning this Embodiment 1. It is a figure showing the influence of the position shift of the light beam limiting means which concerns on this Embodiment 1. FIG. It is a figure showing the effect of the 2nd slit concerning this Embodiment 1. It is a characteristic curve figure showing the characteristic of a general silver salt photosensitive material. It is a figure showing the effect of the 1st slit concerning this Embodiment 2. It is a figure showing the relationship between the kick rate of the 1st slit concerning this Embodiment 2, and a passage rate. It is a figure showing the relationship between the kick rate of the 1st slit concerning this Embodiment 2, and LD drive current / light quantity. It is a figure showing the relationship between the kick rate of the 1st slit concerning this Embodiment 2, and a dynamic range. It is a side view of the conventional exposure apparatus.

Explanation of symbols

10 Exposure system 12 LD
DESCRIPTION OF SYMBOLS 14 Active layer 16 Light-emitting point 18 1st slit board 20 1st slit 22 Movement mechanism 24 Coupling lens 26 2nd slit board 28 2nd slit 30 Movement mechanism 32 2nd lens 40 Beam 42 Flare light

Claims (12)

In an exposure apparatus using a GaN blue semiconductor laser as a light source,
Providing a first restricting means for restricting a passing light beam between an active layer of the semiconductor laser and a coupling lens closest to the active layer;
An exposure apparatus characterized in that the limiting direction of the first limiting means is a direction orthogonal to the active layer of the semiconductor laser. 2. The exposure apparatus according to claim 1, wherein the first restricting unit is movable relative to the light source in a restricting direction. Providing a second restricting means for restricting a passing light beam after the coupling lens;
2. The exposure apparatus according to claim 1, wherein the limiting direction of the second limiting means is a direction along an active layer of the laser crystal. 4. The exposure apparatus according to claim 3, wherein the second restricting unit is movable in a restricting direction. When the opening width in the limiting direction of the first limiting means is D, the distance from the light emitting surface of the active layer to the first limiting means is L, and the beam divergence angle from the light emitting surface is α,
D / {2L · tan (α / 2)} ≦ 2.0
The exposure apparatus according to claim 1, wherein the exposure apparatus has a configuration satisfying the above. In an exposure apparatus using a GaN blue semiconductor laser as a light source,
When the numerical aperture of the coupling lens closest to the light emitting surface of the active layer of the blue semiconductor laser is NA, and the beam divergence angle from the light emitting surface is α,
NA · tan (α / 2) ≦ 2.0
An exposure apparatus having a configuration satisfying the above. Using a GaN-based blue semiconductor laser as a light source,
An image is formed on the photosensitive material using silver halide by irradiation light from the GaN-based blue semiconductor laser,
In an exposure apparatus that performs gradation expression of the image by controlling the driving current of the GaN-based blue semiconductor laser and modulating the emission intensity of the irradiation light,
Providing a first restricting means for restricting a passing light beam between a light emitting point of the active layer of the GaN-based semi-blue conductor laser and a coupling lens closest to the light emitting point;
The limiting direction of the first limiting means is a direction orthogonal to the active layer of the GaN-based blue semiconductor laser,
When the opening width in the limiting direction of the first limiting means is D, the distance from the light emitting point of the active layer to the first limiting means is L, and the spread angle of the beam from the light emitting point is α,
D / {2L · tan (α / 2)} ≦ 1.8
An exposure apparatus characterized by satisfying the requirements. Using a GaN-based blue semiconductor laser as a light source,
An image is formed on the photosensitive material using silver halide by irradiation light from the GaN-based blue semiconductor laser,
In an exposure apparatus that performs gradation expression of the image by controlling the driving current of the GaN-based blue semiconductor laser and modulating the emission intensity of the irradiation light,
When the numerical aperture of the coupling lens closest to the emission point of the active layer of the GaN-based blue semiconductor laser is NA, and the spread angle of the beam from the emission point is α,
NA · tan (α / 2) ≦ 1.8
An exposure apparatus characterized by satisfying the requirements. 9. The exposure according to claim 7, wherein a predetermined driving current is continuously applied to the GaN-based blue semiconductor laser so that the GaN-based blue semiconductor laser emits light in the LED region even in the absence of an image signal. apparatus.
The light-sensitive material using silver halide comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, a cyan-colored red-sensitive silver halide emulsion layer and a non-photosensitive material on a support. In the silver halide color photographic light-sensitive material having a photographic constituent layer composed of at least one hydrophilic hydrophilic colloid layer, the total amount of gelatin coated in the photographic constituent layer is 3 g / m 2 or more and 6 g / m 2 or less, A silver halide color photographic light-sensitive material comprising a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less and a silver chloride content of 90 mol% or more in a yellow-colored blue-sensitive silver halide emulsion layer. The exposure apparatus according to claim 7 or 8. The light-sensitive material using silver halide comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, a cyan-colored red-sensitive silver halide emulsion layer and a non-photosensitive material on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer composed of at least one hydrophilic hydrophilic colloid layer, the total amount of coated silver in the photographic constituent layer is 0.2 g / m 2 or more and 0.5 g / m 2 or less. And a silver halide color photographic light-sensitive material comprising a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less and a silver chloride content of 90 mol% or more in the yellow-colored blue-sensitive silver halide emulsion layer. The exposure apparatus according to claim 7 or 8, characterized in that: The light-sensitive material using silver halide comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, a cyan-colored red-sensitive silver halide emulsion layer and a non-photosensitive material on a support. In the silver halide color photographic light-sensitive material having a photographic constituent layer composed of at least one hydrophilic hydrophilic colloid layer, the total amount of gelatin coated in the photographic constituent layer is 3 g / m 2 or more and 6 g / m 2 or less, The total amount of coated silver in the photographic composition layer is 0.2 g / m 2 or more and 0.5 g / m 2 or less, and the yellow color developing blue-sensitive silver halide emulsion layer has a sphere equivalent diameter of 0.6 μm or less and contains silver chloride. 9. The exposure apparatus according to claim 7, wherein the exposure apparatus is a silver halide color photographic light-sensitive material containing a silver halide emulsion having a ratio of 90 mol% or more.

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