JP2004151706A - Silver halide color reversal photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color reversal photographic sensitive material having both particularly superior flesh color reproducibility and faithful color reproducibility and ensuring a small hue change to subject's light and shade or unevenness in exposure and to provide a color reversal photographic sensitive material having improved suitability to various light sources and ensuring improved color temperature dependence of a light source. <P>SOLUTION: The silver halide color reversal photographic sensitive material has at least one each of the following interimage effect imparting layers (a) and (b). When the photographic sensitive material is exposed with "flesh color" light having a spectral reflectance distribution and developed, in a "flesh color" image reproduced by the photographic sensitive material, the ratio (C*<SB>70</SB>/C*<SB>50</SB>) of chroma C*<SB>70</SB>at lightness L*=70 to chroma C*<SB>50</SB>at lightness L*=50 expressed by the CIE Lab color system is ≥0.7. The interimage effect imparting layer (a) comprises a shortwave green-sensitive silver halide emulsion having a centroid wavelength of its spectral sensitivity distribution of 500-560 nm. The interimage effect imparting layer (b) comprises a red-sensitive silver halide emulsion having a centroid wavelength of its spectral sensitivity distribution of 580-700 nm. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a color reversal photographic light-sensitive material with improved color reproducibility, and more particularly to a color reversal photographic light-sensitive material that is excellent in skin color reproducibility and color fidelity reproducibility and has a small hue change with respect to subject brightness and exposure variations. Is. The present invention also relates to a color reversal photographic light-sensitive material having improved various light source suitability and color temperature dependency of the light source.

  In color reversal photographic light-sensitive materials, the color reproducibility is an important characteristic. Conventionally, various attempts have been made to improve color reproducibility such as correction of sub-absorption of a color material by masking and use of an interimage effect.

  In particular, the reproducibility of “skin color” is important in fields such as fashion and portrait photography, and improvement has been demanded.

  However, in the reproduction of human skin color, there is a difference between the actual skin color and the preferred skin color to be reproduced (for example, the normal skin color prefers higher saturation than the actual skin color, but the drawbacks such as acne are conspicuous It is not always appropriate to faithfully reproduce the actual skin. In addition, the human eye is very sensitive to skin color and recognizes small color differences that are not noticeable in normal colors as differences in the case of skin colors, so it requires very precise control of color reproduction. There are difficulties.

  As a technology for improving the color reproducibility of the skin color, for example, a color reversal photographic element having an inter-image effect control means and reproducing red with high relative saturation and yellow red (skin color) with substantially low relative saturation Is disclosed (for example, see Patent Document 1). However, in the color reversal photographic element of the present invention, only the relative saturation of yellowish red (skin color) is specified, but nothing is mentioned about the hue of the skin color.

There is also disclosed a color reversal photographic light-sensitive material that has an inter-image effect control means and defines the saturation and hue of skin color and reddish skin color (for example, see Patent Document 2). However, even in the present invention, there is no provision regarding the saturation ratio between skin colors having different lightnesses, and it is not sufficient for improving the skin color. In this invention, as one of the inter image effect control means, there is a description that an inter image effect imparting layer having a spectral sensitivity distribution different from that of the blue, green and red main photosensitive layers may be provided. No means are disclosed, and there is no description that discloses the usefulness of the two types of interimage effect imparting layers of the present invention.
US Pat. No. 5,378,590 US Pat. No. 6,048,673

  An object of the present invention is to provide a color reversal photographic light-sensitive material having improved color reproducibility, and in particular, a color excellent in skin color reproducibility and color fidelity reproducibility, and having a small hue change with respect to light and darkness of an object and variations in exposure. The object is to provide a reversal photographic material. Another object of the present invention is to provide a color reversal photographic light-sensitive material having improved light source suitability and color temperature dependency of the light source.

  The object of the present invention has been achieved by the following means.

(1) A blue-sensitive silver halide emulsion layer containing a yellow color coupler, a green-sensitive silver halide emulsion layer containing a magenta color coupler, and a red-sensitive silver halide emulsion layer containing a cyan color coupler on a transparent support. In the silver halide color reversal photographic light-sensitive material having at least one layer, the photographic light-sensitive material imparts the following interimage effects in addition to the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers. In a “skin color” image reproduced with the photographic light-sensitive material when the photographic light-sensitive material is exposed to “skin color” light having the spectral distribution shown in Table 1 and then developed, a chroma ^C _{* 70} in lightness ^L * = 70 represented by the Lab color system, the lightness ^L * = ratio of chroma ^C _{* 50} at _{^{50 (C * 70 / C *}} 50) is And wherein the at .7 above, silver halide color reversal photographic material.

(A) An inter-image effect imparting layer containing a short-wave green-sensitive silver halide emulsion having a spectral sensitivity distribution having a centroid wavelength of 500 nm or more and 560 nm or less.

(B) An inter-image effect imparting layer containing a red-sensitive silver halide emulsion having a spectral sensitivity distribution with a centroid wavelength of 580 nm to 700 nm.

(2) and the chroma ^C _{* 20} in lightness ^L * = 20, a ratio of the chroma ^C _{* 50} in lightness _{^{L * = 50 (C * 20}} / C * 50) is equal to or less than 0.7 The silver halide color reversal photographic light-sensitive material according to (1).

(3) The standard deviation of the hue angle in the CIE Lab color system of the “skin color” image reproduced with the photographic light-sensitive material is within 1.0 in the range of lightness L ^* = 20 to 70, The silver halide color reversal photographic light-sensitive material according to (1) or (2).

(4) CIE Lab of a “gray” image reproduced by the photographic material when the photographic material is exposed to light having the “gray” spectral reflectance distribution shown in Table 2 below and then developed. The halogen according to any one of (1) to (3), wherein the saturation C * value in the color system is 0 or more and 10 or less in the range of lightness L ^* = 20 to 70 Silver halide color reversal photographic light-sensitive material.

  (5) The centroid wavelength of the spectral sensitivity distribution of the red-sensitive silver halide emulsion layer is 580 nm or more and 630 nm or less, and the centroid wavelength of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm or more and 560 nm or less. The silver halide color reversal photographic light-sensitive material according to any one of (1) to (4), wherein:

  The color reversal photographic light-sensitive material of the present invention has excellent skin color reproducibility and faithful color reproducibility, can reduce the hue change due to light and dark of the subject and variations in exposure, and has improved the suitability of various light sources and the color temperature dependency of the light sources. A color reversal photographic light-sensitive material can be provided.

  The silver halide color reversal photosensitive material of the present invention will be described in detail below. The color reversal light-sensitive material of the present invention comprises a blue-sensitive silver halide emulsion layer containing a yellow coloring coupler, a green-sensitive silver halide emulsion layer containing a magenta coloring coupler, and a red sensitivity containing a cyan coloring coupler on a support. Each of the silver halide emulsion layers, and each of the following (a) and (b) interimage effect imparting layers.

(A) An inter-image effect imparting layer containing a short-wave green-sensitive silver halide emulsion having a spectral sensitivity distribution having a centroid wavelength of 500 nm or more and 560 nm or less.

(B) An inter-image effect imparting layer containing a red-sensitive silver halide emulsion having a spectral sensitivity distribution with a centroid wavelength of 580 nm to 700 nm.

In the present invention, a red-sensitive emulsion layer, a green-sensitive emulsion layer, an inter-image effect imparting layer containing the short-wave green-sensitive silver halide emulsion of the present invention (hereinafter referred to as a short-wave green-sensitive inter-image effect imparting layer), the red of the present invention The center-of-gravity wavelengths λr, λg, λic, and λir of the spectral sensitivity distribution of an interimage effect-imparting layer (hereinafter referred to as a red-sensitive interimage effect-imparting layer) containing a light-sensitive silver halide emulsion can be obtained from the following equations, respectively.

  Here, Sn (λ) is a spectral sensitivity distribution at a color density of 1.0 of each color-sensitive layer. When the photosensitive emulsion layer does not develop color, Sn (λ) is a single layer using the emulsion. The coated sample can be developed from silver and obtained from the spectral response result giving this blackened silver concentration of 0.2. In many cases, the center-of-gravity wavelength of the spectral sensitivity distribution corresponds to the absorption wavelength of the J-aggregate of the spectral sensitizing dye adsorbed on the emulsion, and often coincides with the wavelength giving the maximum value of the spectral sensitivity distribution.

  The light-sensitive material of the present invention is subjected to color reversal processing. Specific processing methods are typically Fuji Photo Film Co., Ltd. Process CR-56 and “Development Processing A” described below.

(Development A)
In the evaluation, a commercially available color reversal film (Provia 100F manufactured by Fuji Photo Film) that was completely exposed to light was run at a ratio of 1: 1 until the replenishment amount was 4 times the tank capacity. Use later. (In the following, liter is expressed as “L” and milliliter as “mL”.)
Processing process Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ℃ 12L 2200mL / m ²
First washing 2 minutes 38 ℃ 4L 7500mL / m ²
Inversion 2 minutes 38 ℃ 4L 1100mL / m ²
Color development 6 minutes 38 ℃ 12L 2200mL / m ²
Pre-bleaching 2 minutes 38 ℃ 4L 1100mL / m ²
Whitening 6 minutes 38 ℃ 12L 220mL / m ²
Settling time 4 minutes 38 ℃ 8L 1100mL / m ²
Second washing 4 minutes 40 ℃ 8L 7500mL / m ²
Final rinse 1 minute 25 ° C 2L 1100mL / m ²
The composition of each treatment solution was as follows.

[First developer] [Tank solution] [Replenisher]
Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 1.5 g 1.5 g
Diethylenetriaminepentaacetic acid pentasodium salt 2.0g 2.0g
Sodium sulfite 30g 30g
Hydroquinone monosulfonate 20g 20g
Potassium carbonate 15g 20g
Potassium bicarbonate 12g 15g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g
Potassium bromide 2.5g 1.4g
Potassium thiocyanate 1.2g 1.2g
Potassium iodide 2.0 mg −
Diethylene glycol 13g 15g
Add water 1000mL 1000mL
pH 9.65 9.65
The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversing liquid] [Tank liquid] [Replenisher]
Nitrilo-N, N, N-trimethylenephosphonic acid tank solution ・ Same stannous chloride dihydrate 1.0g as 5sodium salt 3.0g
Sodium hydroxide 8g
Glacial acetic acid 15mL
1000mL with water
pH 6.00
The pH was adjusted with acetic acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher]
Nitrilo-N, N, N-trimethine phosphonic acid pentasodium salt 2.0 g 2.0 g
Sodium sulfite 7.0g 7.0g
Trisodium phosphate 12 hydrate 25g 25g
Potassium bromide 1.0 g −
Potassium iodide 50mg −
Sodium hydroxide 10.0g 10.0g
Citrazic acid 0.5g 0.5g
N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline, 3/2 sulfuric acid,
Monohydrate 9.0g 9.0g
3,6-dithiaoctane-1,8-diol 0.6 g 0.7 g
Add water 1000mL 1000mL
pH 11.85 12.00
The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank liquid] [Replenisher]
Ethylenediaminetetraacetic acid, disodium salt, dihydrate 8.0g 8.0g
Sodium sulfite 6.0g 8.0g
1-thioglycerol 0.4g 0.4g
Formaldehyde sodium bisulfite adduct 25g 25g
Add water 1000mL 1000mL
pH 6.30 6.10
The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher solution]
Ethylenediaminetetraacetic acid, disodium salt, dihydrate 2.0g 4.0g
Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / Dihydrate 120 g 240 g
Potassium bromide 100g 200g
Ammonium nitrate 10g 20g
Add water 1000mL 1000mL
pH 5.70 5.50
The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher solution]
Ammonium thiosulfate 80g Same as sodium sulfite 5.0g Same as above Sodium bisulfite 5.0g Same as above 1000ml water same as above pH 6.60
The pH was adjusted with acetic acid or aqueous ammonia.

[Stabilizer] [Tank fluid] [Replenisher]
1,2-Benzisothiazolin-3-one 0.02g 0.03g
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g
Polymaleic acid (average molecular weight 2,000) 0.1g 0.15g
Add water 1000mL 1000mL
pH 7.0 7.0
However, in the case of measuring the spectral sensitivity distribution of the layer not containing the coupler, the black and white through only the first development, the first water washing, the fixing and the second water washing among the steps of the “development processing A” described above. Evaluate by development processing.

  The color reversal photographic light-sensitive material of the present invention preferably has a spectral sensitivity distribution represented by a cyan image, that is, a centroid wavelength of a spectral sensitivity distribution of a red-sensitive silver halide emulsion layer containing a cyan coloring coupler, in the range of 580 nm to 630 nm. More preferably, it exists in 620 nm or less. The center of gravity wavelength of the spectral sensitivity distribution represented by the magenta image, that is, the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer containing the magenta coloring coupler is preferably 520 nm to 560 nm, and more preferably 530 nm to 550 nm.

The color reversal photographic light-sensitive material of the present invention has a center-of-gravity wavelength of spectral sensitivity distribution in the range of 500 nm to 560 nm, preferably 510 nm to 540 nm, in addition to the green-sensitive silver halide emulsion layer, and contains silver iodide. At least one short-wave green-sensitive interimage effect imparting layer containing a silver halide emulsion capable of imparting an interimage effect. In the color reversal photographic light-sensitive material of the present invention, the centroid wavelength of the spectral sensitivity distribution of the green-sensitive layer and the centroid wavelength of the spectral sensitivity distribution of the short-wave green-sensitive inter-image effect imparting layer satisfy the above-mentioned ranges, respectively. The centroid wavelength of the spectral sensitivity distribution is preferably larger than the centroid wavelength of the spectral sensitivity distribution of the shortwave green-sensitive interimage effect imparting layer. The silver halide emulsion contained in the short wave green-sensitive interimage effect-imparting layer may be photosensitive or non-photosensitive, but is a silver halide containing 1 mol% or more of silver iodide. A silver halide containing 5 mol% or more of silver iodide is more preferable. The silver halide emulsion contained in the short-wave green-sensitive interimage effect-imparting layer is not particularly limited as long as the silver halide contains 1 mol% or more of silver iodide. Silver iodobromide containing at least mol% is preferred. The coating amount of silver of the short wave green-sensitive interimage effect imparting layer is preferably 0.1 to 1.0 g / m ^2, and still more preferably from 0.2 to 0.7 g / m ² .

  The short-wave green-sensitive interimage effect imparting layer preferably does not substantially form a magenta image. A magenta coupler may also be included, but in that case, it is preferably 1/5 mol% or less, more preferably 1/10 mol% or less of the entire magenta coupler contained in the green-sensitive silver halide emulsion layer.

The color reversal photographic light-sensitive material of the present invention is a silver halide emulsion having a centroid wavelength of spectral sensitivity distribution at 580 nm to 700 nm, preferably 590 nm to 670 nm, and capable of giving an interimage effect by containing silver iodide. At least one red-sensitive interimage effect imparting layer. In the color reversal photographic light-sensitive material of the present invention, the center-of-gravity wavelength of the spectral sensitivity distribution of the red-sensitive layer and the center-of-gravity wavelength of the spectral sensitivity distribution of the red-sensitive interimage effect imparting layer satisfy the above-described ranges, respectively. It is preferable that the centroid wavelength of the sensitivity distribution is smaller than the centroid wavelength of the spectral sensitivity distribution of the red-sensitive interimage effect imparting layer. The silver halide emulsion contained in the red-sensitive interimage effect-imparting layer may be photosensitive or non-photosensitive, but is preferably a silver halide containing 1 mol% or more of silver iodide. More preferably, the silver halide contains 5 mol% or more of silver iodide. The silver halide emulsion contained in the red-sensitive interimage effect imparting layer is not particularly limited as long as the silver halide contains 1 mol% or more of silver iodide, but 5 mol of silver iodide is not particularly limited. Silver iodobromide containing at least% is preferred. The silver coating amount of the red-sensitive interimage effect imparting layer is preferably 0.1 to 1.0 g / m ^2, and still more preferably from 0.2 to 0.7 g / m ^2.

  The red-sensitive interimage effect imparting layer preferably does not substantially form a cyan image. A cyan coupler may be contained, but in that case, it is preferably 1/5 mol% or less, more preferably 1/10 mol% or less of the whole cyan coupler contained in the red-sensitive silver halide emulsion layer.

  The short-wave green-sensitive interimage effect-imparting layer and red-sensitive interimage effect-imparting layer can be arranged at arbitrary positions, but are preferably arranged close to the red-sensitive layer. In a general color reversal photographic light-sensitive material, a blue-sensitive layer is arranged at a position farthest from the support, followed by a green-sensitive layer and a red-sensitive layer at a position closest to the support. It is preferable to arrange at a position closer to the support than the sensitive layer, more preferably at a position closer to the support than the green sensitive layer, and further to be disposed between the red sensitive layer and the support. Preferably, the red-sensitive layer, the red-sensitive inter-image effect imparting layer, the short wave green-sensitive inter-image effect imparting layer, and the support are most preferably arranged in this order. It is preferable that an undercoat layer / antihalation layer is provided between the short wave green-sensitive interimage effect imparting layer and the support from the side close to the support.

In the short-wave green-sensitive and red-sensitive interimage effect-imparting layer and / or in the intermediate layer separating the inter-image effect-imparting layer from other color-sensitive layers, there is a competitive compound (color development in competition with the image-forming coupler). It is preferable to use a compound that reacts with the oxidized drug and does not form a dye image. Competing compounds include reducing compounds such as hydroquinones, catechols, hydrazines, sulfonamidophenols, or compounds that couple with oxidized color developer but do not substantially form a color image (for example, German Patent 1 155,675, British Patent 861,138, U.S. Pat. Nos. 3,876,428 and 3,912,513, or a non-colored coupler, or JP-A-6-83002 And a coupler in which the produced dye flows out during the processing step). The amount of the competitive compound added is 0.01 g to 10 g, preferably 0.10 g to 5.0 g, per 1 m ² of the photosensitive material.

  The spectral reflectances of “skin color” and “gray” used in the present invention are as shown in Tables 1 and 2, respectively. The measured value of Munsell N5 color chart was used for the spectral reflectance of “gray”.

  In the present invention, the above spectral reflectance was multiplied by the spectral distribution of ISO daylight (D55) to calculate the spectral distribution (relative spectral luminance) of each color under standard illumination. The above spectral distribution is generated using a spectral sensitometer that creates an arbitrary spectral distribution by electrically controlling the transmittance of each liquid crystal segment using an intensity-modulated mask created by arranging liquid crystal panels in stripes. Can be made. The spectral sensitometer device for generating the spectral distribution can be produced based on a report by Enomoto et al. In the 1990 Annual Meeting of SPSTJ '90. FIG. 1 of US Pat. No. 6,048,673 discloses a principle diagram of an apparatus mainly composed of an optical system and a schematic diagram of a liquid crystal mask. A xenon arc lamp with high brightness is used as the light source, and slit light that is long in the grating direction of the diffraction grating is obtained by an optical system using a cylindrical lens. The light split by the transmission diffraction grating becomes a spectral plane having a wavelength range of 400 nm to 700 nm on the dispersion plane. A liquid crystal panel composed of 60 segments, each having 5 nm as one segment, is placed on this spectrum surface, and the transmittance is controlled every 5 nm to obtain a target spectral distribution. Mixed color slit light is produced on the exposure surface, and exposure is performed by scanning a light-sensitive material on which optical wedges are stacked in a direction perpendicular to the slit light.

  The measurement of “skin color” and “gray” reproduced with the light-sensitive material of the present invention was performed under observation conditions based on a color matching experiment employing a double field of view at the 1931 meeting of the CIE (International Lighting Commission). . The CIE Lab value was calculated using a CIE 1976 (L *, a *, b *) uniform perceptual color space calculation method. For more detailed explanations of these, for example, Chapter 4 of the “New Color Science Handbook” published by the University of Tokyo Press (1980) can be referred to.

  In the present invention, in order to evaluate “skin color” and “gray” images, correction is performed so that the C * value represented by the CIE Lab value of the “gray” image is 0.5 or less at L * = 40. There is a need to. For example, the correction can be performed by using a commercially available color correction filter. Alternatively, as in the method described in US Pat. No. 5,378,590, the tristimulus values X, Y, and Z at L * = 40 of the “gray” image are rescaled as the reference white, and “skin color” and “ Although the CIE Lab value of the “gray” image can be recalculated and evaluated, it is preferable to correct during exposure.

The ratio of the saturation C ^* _{70 at} L ^* = 70 represented by the CIE Lab value of the “skin color” image reproduced with the light-sensitive material of the present invention and the saturation C ^* ₅₀ at L ^* = 50 (C ^* ₇₀ / C ^* ₅₀ ) is 0.7 or more, preferably 0.75 or more, and more preferably 0.8 or more. The larger this value, the higher the saturation of the high brightness skin color, and the more beautiful skin color reproduction can be obtained.

The ratio of the saturation C ^* _{20 at} L ^* = 20 represented by the CIE Lab value of the “skin color” image reproduced with the light-sensitive material of the present invention and the saturation C ^* ₅₀ at L ^* = 50 (C ^* ₂₀ / C ^* ₅₀ ) is preferably 0.7 or more, more preferably 0.75 or more, and further preferably 0.8 or more. The larger this value, the smaller the decrease in the saturation of the low brightness skin color, and the more beautiful skin color reproduction can be obtained.

  The standard deviation value of the hue angle represented by the CIE Lab value of the “skin color” image reproduced with the light-sensitive material of the present invention is preferably within 1.0 in the range of L * = 20 to 70. It is more preferably within 0.6, and further preferably within 0.4. The smaller this value, the smaller the hue change of the skin color over the range from low lightness to high lightness.

  The C * value represented by the CIE Lab value of the “skin color” image reproduced with the light-sensitive material of the present invention is preferably 10 or more and 35 or less, and 15 or more and 30 or less in the range of L * = 20 to 70. More preferably it is.

  The hue angle value represented by the CIE Lab value of the “skin color” image reproduced with the light-sensitive material of the present invention is preferably 20 degrees or more and 70 degrees or less in the range of L * = 20 to 70, and 30 degrees. More preferably, it is within 60 degrees.

  The C * value represented by the CIE Lab value of the “gray” image reproduced with the light-sensitive material of the present invention is preferably 0 or more and 10 or less in the range of L * = 20 to 70, but 0 or more and 7 or less. Is more preferably 0 or more and 5 or less. The smaller this value, the better the gray reproducibility over the range from low to high brightness.

  As is clear from the spectral reflectance distribution data in Table 1, the “skin color” is yellowish red. Therefore, the “skin color” image reproduced when the photographic photosensitive material is exposed and developed with “skin color” light has a sensitivity of the red color sensitive layer to the blue / green color sensitive layer with respect to the “gray” image. Reproduced relatively higher than the sensitivity. This suggests that controlling the bidirectional interimage effect between the blue / green color sensitive layer and the red color sensitive layer is important for good skin color reproducibility. In the present invention, two inter-image effect-imparting layers of short wave green (blue / green) color sensitivity and red color sensitivity are installed, so that a bidirectional color between the blue / green color sensitive layer and the red color sensitive layer can be obtained. This technology provides a technique for controlling the inter-image effect, and this technology has made it possible to achieve excellent skin color reproduction.

  The light-sensitive material of the present invention may have at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer on the support. It is preferable to coat and configure in this order from the far side, but a different order may be used. In the present invention, it is preferable to coat a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer in this order from the side close to the support, and each color-sensitive layer has a sensitivity. It is preferable that the unit structure includes two or more different light-sensitive emulsion layers. In particular, three layers each comprising three light-sensitive emulsion layers, a low-sensitivity layer, a medium-sensitivity layer, and a high-sensitivity layer, from the side close to the support. A unit configuration is preferred. These are described in JP-B-49-15495, JP-A-59-202464, and the like.

  As one of the preferred embodiments of the present invention, an undercoat layer / antihalation layer / first intermediate layer / shortwave green-sensitive interimage effect imparting layer / red sensitive interimage effect imparting layer / second intermediate layer on a support. / Red-sensitive emulsion layer unit (consisting of three layers: low-sensitivity red-sensitive layer / medium-sensitive red-sensitive layer / high-sensitivity red-sensitive layer from the side close to the support) / third intermediate layer / green-sensitive emulsion layer unit (support From the side close to the low sensitivity green sensitive layer / medium sensitive green sensitive layer / high sensitive green sensitive layer) / fourth intermediate layer / yellow filter layer / blue sensitive emulsion layer unit (low from the side close to the support) A photosensitive element in which each layer is applied in the order of (sensitive blue sensitive layer / medium sensitive blue sensitive layer / high sensitive blue sensitive layer) / first protective layer / second protective layer.

  Each of the first, second, third, and fourth intermediate layers may be a single layer or may have two or more layers. The second intermediate layer is further divided into two or more layers, and the layer directly adjacent to the red-sensitive layer preferably contains yellow colloidal silver. Similarly, the third intermediate layer is also composed of two or more layers, and the layer directly adjacent to the green-sensitive layer preferably contains yellow colloidal silver. It is also preferable to further have a fifth intermediate layer between the yellow filter layer and the blue-sensitive emulsion layer unit.

  The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-113438, 59-113440, 61-20037, and 61-20038. Etc. may be included, and a color mixing inhibitor may be included as normally used.

  It is also preferable that the protective layer has a three-layer configuration of a first protective layer to a third protective layer. When the protective layer is composed of two or three layers, the second protective layer preferably contains fine grain silver halide having an average sphere equivalent diameter of 0.10 μm or less. The silver halide is preferably silver bromide or silver iodobromide.

  The average equivalent sphere diameter is an average value of diameters of spheres having a volume equivalent to that of individual silver halide grains.

  The photographic light-sensitive material of the present invention includes a blue-sensitive interimage effect-imparting layer in addition to the short-wave green-sensitive interimage effect-providing layer and the red-sensitive interimage effect-providing layer, and a blue, green, and red-sensitive main photosensitivity. It can also be placed adjacent or close to the layer. The blue sensitive interimage effect imparting layer is preferably disposed between the yellow filter layer and the blue sensitive emulsion layer unit. The blue-sensitive inter-image effect imparting layer is a short-wave blue-sensitive layer in which the centroid wavelength of the spectral sensitivity distribution of the blue-sensitive main photosensitive layer is larger than the centroid wavelength of the spectral sensitivity distribution of the blue-sensitive inter-image effect imparting layer. preferable.

  The light-sensitive material of the present invention comprises an image forming coupler. An image-forming coupler is a coupler that forms an image-forming dye by coupling an oxidized form of an aromatic primary amine color developer, and generally uses a yellow coupler, a magenta coupler, and a cyan coupler to produce a color image. obtain.

  The image-forming coupler of the present invention is preferably used by being added to a photosensitive emulsion layer that is sensitive to light having a complementary color relationship with the coloring hue of the coupler. That is, the yellow coupler is added to the blue sensitive emulsion layer, the magenta coupler is added to the green sensitive emulsion layer, and the cyan coupler is added to the red sensitive emulsion layer. In addition, for the purpose of improving the shadow description, a coupler having no complementary color relationship may be mixed and used (for example, a cyan coupler is used in combination with the green sensitive emulsion layer).

  Preferred examples of the image-forming coupler used in the light-sensitive material of the present invention include the following.

  Yellow couplers; couplers represented by formulas (I) and (II) in European Patent 502,424A; couplers represented by formulas (1) and (2) in European Patent 513,496A (for example, Y- 28 (18 pages)); a coupler represented by the formula (I) of claim 1 of European Patent 568,037A; general formula of columns 45 to 55 of column 1 of US Pat. No. 5,066,576 A coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; a coupler described in claim 1 on page 40 of European Patent 498,381A1 ( For example, D-35); a coupler represented by the formula (Y) on page 4 of European Patent 447,969A1 (for example, Y-1, Y-54); a column of US Pat. No. 4,476,219 7 36-5 Such coupler represented by formula (II) ~ (IV) lines.

  Magenta couplers; couplers described in JP-A-3-39737 (for example, L-57, L-68, L-77); couplers described in European Patent 456,257A (for example, A-4-63, A -73, A-4-75); couplers described in EP 486,965A (for example, M-4, M-6, M-7) couplers described in EP 571,959A (For example, M-45) coupler described in JP-A-5-204106 (for example, M-1); coupler described in JP-A-4-362631 (for example, M-22) described in JP-A-11-119393 Couplers represented by the general formula (MC-1) (for example, CA-4, CA-7, CA-12, CA-15, CA-16, CA-18).

  Cyan coupler; coupler described in JP-A-4-204843 (for example, CX-1,3,4,5,11,12,14,15); coupler described in JP-A-4-43345 (for example, C- 7, 10, 34, 35 and (I-1), (I-17)); couplers represented by general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385; Couplers represented by the general formula (PC-1) described in JP-A-11-119393 (for example, CB-1, CB-4, CB-5, CB-9, CB-34, CB-44, CB-49, CB-51); couplers represented by the general formula (NC-1) described in JP-A-11-119393 (for example, CC-1, CC-17) and the like.

  These couplers can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (in combination with a low-boiling solvent if necessary), emulsified and dispersed in an aqueous gelatin solution, and added to a silver halide emulsion. An oil droplet dispersion method is preferred.

  Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. In addition, specific examples of the latex dispersion process, effect, and impregnation latex as one of polymer dispersion methods are described in US Pat. No. 4,199,363, West German Patent Application (OLS) 2,541,274. No. 2,541,230, Japanese Examined Patent Publication No. 53-41091, and European Patent Publication No. 029104, and dispersion with an organic solvent soluble polymer is described in PCT International Publication No. WO 88/00723. It is described in the specification.

  Examples of the high-boiling solvent that can be used in the aforementioned oil-in-water dispersion method include phthalate esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, bis (2-ethylhexyl) phthalate, decyl phthalate, bis (2,4 -Di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl) Phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, bis (2-ethylhexyl) phenyl phosphate), benzoic acid ester Tells (eg, 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecanamide, N, N-diethyllaurylamide) , N, N, N, N-tetrakis (2-ethylhexyl) isophthalamide), alcohols or phenols (for example, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic esters (for example, , Dibutoxyethyl succinate, bis (2-ethylhexyl) succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl sylate), aniline derivatives (for example, N, N- Dibutyl -Butoxy-5-tert-octylaniline), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic acid esters (for example, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols ( For example, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4 -Di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (for example, bis (2-ethylhexyl) phosphoric acid, diphenylphosphoric acid), etc. In addition to the above high-boiling solvents, For example, a compound described in JP-A-6-258803 has a high boiling point. It is also preferable to use as the solvent.

  The ratio of the amount of the high-boiling organic solvent used in combination with the coupler is preferably 0 to 2.0 by mass ratio, more preferably 0 to 1.0, and particularly preferably 0 to 0.4.

  As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more and about 160 ° C. or less (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The content of the coupler in the light-sensitive material is 0.01 g to 10 g per 1 m ² as the total mass of each of the yellow coupler, magenta coupler and cyan coupler, preferably 0.1 g to ² g per 1 m ^2. 1 × 10 ⁻³ mol to 1 mol per mol of silver halide is suitable, preferably 2 × 10 ⁻³ mol to 3 × 10 ⁻¹ mol.

When the photosensitive layer has a unit constitution composed of two or more photosensitive emulsion layers having different sensitivities, the coupler content of the present invention per mole of silver halide is 2 × 10 ⁻³ mol to 2 × in the lowest sensitivity layer. 10 ⁻¹ mol is preferable, and in the high sensitivity layer, 3 × 10 ⁻² mol to 3 × 10 ⁻¹ mol is preferable.

  In the light-sensitive material of the present invention, a competitive compound (a compound that reacts with an oxidized color developer in competition with an image-forming coupler and does not form a dye image) may be used in combination. Competing compounds include reducing compounds such as hydroquinones, catechols, hydrazines, sulfonamidophenols, or compounds that couple with oxidized color developer but do not substantially form a color image (for example, German Patent 1 155,675, British Patent 861,138, U.S. Pat. Nos. 3,876,428, 3,912,513, or a non-colored coupler, And couplers in which the produced dye flows out during the processing step, as disclosed in JP-A-6-83002.

  The light-sensitive material of the present invention may have a non-color-forming intermediate layer in the same color-sensitive photosensitive unit, and the intermediate layer may further contain a compound that can be selected as the competitive compound. preferable.

  The light-sensitive material of the present invention reacts with formaldehyde gas described in US Pat. Nos. 4,411,987 and 4,435,503 in order to prevent deterioration of photographic performance due to formaldehyde gas. It is preferable that the photosensitive material contains a compound that can be immobilized.

  The emulsion used in the silver halide photographic light-sensitive material of the present invention preferably contains tabular silver halide grains having an aspect ratio of 1.5 to 100. Here, tabular silver halide grains (also referred to as “tabular grains”) are a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points are mirror images on both sides of the (111) plane. This tabular grain is composed of two main surfaces parallel to each other and side surfaces connecting these main surfaces. When the tabular grains are viewed from above with respect to the main surface, the main surface has a triangular shape, a hexagonal shape, or a round shape in which these are rounded. A hexagonal, circular shape has circular main surfaces parallel to each other.

  The aspect ratio of tabular grains refers to a value obtained by dividing grain diameter by thickness. The particle thickness is measured by depositing metal from the diagonal direction of the particle together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating with reference to the shadow length of the latex. Easy to do.

  The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel main surface of the particle.

  The projected area of the particles can be obtained by measuring the area on the electron micrograph and correcting the photographing magnification. The diameter of the tabular grains is preferably 0.3 to 5.0 μm. The thickness of the tabular grains is preferably 0.05 to 0.5 μm.

  In the tabular grains used in the present invention, the sum of their projected areas preferably accounts for 50% or more, particularly preferably 80% or more, based on the sum of the projected areas of all silver halide grains in the emulsion. Furthermore, the aspect ratio of the tabular grains occupying these constant areas is preferably 1.5 or more and less than 100. More preferably, it is 2 or more and less than 20, more preferably 2 or more and less than 8.

  Further, more preferable results may be obtained when monodispersed tabular grains are used. The structure and production method of monodispersed tabular grains follow the description of, for example, JP-A No. 63-151618. To simply describe the shape, 70% or more of the total projected area of silver halide grains is A tabular silver halide having a hexagonal shape in which the ratio of the side having the maximum length to the length of the side having the minimum length on the main surface is 2 or less and having two parallel surfaces as the outer surface Furthermore, the coefficient of variation of the grain diameter distribution of the hexagonal tabular silver halide grains [diversity of the grain diameter (standard deviation) represented by the circle equivalent diameter of the projected area divided by the mean grain diameter] The value obtained by multiplying by 100] has a monodispersity of 20% or less.

  Further, the tabular grains used in the present invention more preferably have dislocation lines. The dislocations of tabular grains are described in, for example, J. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. Japan. 35, 213, (1972), and can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method in the cooled state. In this case, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, the observation using a high-voltage electron microscope (acceleration voltage of 200 kV or more for a particle having a thickness of 0.25 μm) should be observed more clearly. Can do. From the photograph of the particles obtained by such a method, the position of dislocation for each particle when viewed from the direction perpendicular to the main plane can be obtained.

  The position of the dislocation line of the tabular grain used in the present invention is generated from the distance of x% of the length from the center to the side to the side in the major axis direction of the tabular grain. Is 10 ≦ x <100, more preferably 30 ≦ x <98, and still more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocation lines start is similar to the particle shape, but is not completely similar and may be distorted. The direction of the dislocation line is roughly from the center to the side, but it is often meandering.

  Regarding the number of dislocation lines of the tabular grains used in the present invention, it is preferred that 50% (number) or more of grains containing 10 or more dislocations are present. More preferably, particles containing 10 or more dislocation lines are 80% (number) or more, particularly preferably particles containing 20 or more dislocation lines are 80% (number) or more.

  A method for producing tabular grains used in the present invention will be described. The tabular grains used in the present invention are "Theory and Practice of Photography" by Cleeve (Cleve, Photography Theory and Practice (1930)), page 13; Gatoff, Photographic Science and Engineering (Gutuff, Photographic Science and Engineering). 14, 248-257, (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and the United Kingdom. It can be prepared by improving the method described in the specification such as Japanese Patent No. 2,112,157.

  For the tabular silver halide grains used in the present invention, any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide.

  The silver halide emulsion used in the present invention may have a multiple structure with respect to the distribution of silver halide in the grains. For example, it may have a quintuple structure. Here, the structure means that the structure has a distribution of silver iodide, and means that the silver iodide content differs between each structure by 1 mol% or more, more preferably by 2 mol% or more. The structure regarding the silver iodide distribution can be basically obtained by calculation from the prescription value in the grain preparation process. The change in the silver iodide content at the interface between the structures can be abrupt or gentle. In order to confirm these, it is necessary to consider the measurement accuracy in analysis, but the EPMA method (Electron Probe Micro Analyzer method) is usually effective. To make an elemental analysis of a very small region irradiated with an electron beam by preparing a sample in which emulsion grains are dispersed so as not to contact each other and analyzing the X-rays emitted when the sample is irradiated with an electron beam Can do. The measurement at this time is preferably performed by cooling to a low temperature in order to prevent sample damage due to the electron beam. The silver iodide distribution in the grains when the tabular grains are viewed from the direction perpendicular to the main surface can be analyzed by the same method, but the cross section of the tabular grains can be obtained by solidifying the specimen and using a sample cut into ultrathin sections with a microtome. Intragranular silver iodide distribution in can also be analyzed.

  In the nucleation step of grain formation, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used. Performing nucleation at a high pBr described in the specification of No. 014 and performing nucleation in a short time as described in JP-A-2-222940 are extremely effective in preparing tabular grains. In the ripening step, it is carried out in the presence of a low concentration base described in US Pat. No. 5,254,453, and at a high pH described in US Pat. No. 5,013,641. This may be effective in the aging process.

  U.S. Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, 5,210,013, and The method for forming tabular grains using the polyalkylene oxide compound described in each specification of No. 252,453 is preferably used in the present invention.

  In order to obtain monodispersed tabular grains having a large aspect ratio, gelatin may be additionally added during grain formation. At this time, the gelatin used is chemically modified gelatin described in JP-A-10-148897 and JP-A-11-143002, or US Pat. No. 4,713,320 and US Pat. No. 4,942,120. Gelatin with a low methionine content described in the specification is preferred. In particular, the former chemically modified gelatin is characterized in that at least two carboxyl groups are newly introduced when the amino group in the gelatin is chemically modified. It is preferable to use it. The chemically modified gelatin is preferably added before the growth step, more preferably immediately after nucleation. The addition amount is 50% or more, preferably 70% or more with respect to the mass of the total dispersion medium during particle formation.

Examples of the silver halide solvent that can be used in the present invention include U.S. Pat. Nos. 3,271,157, 3,531,286, and 3,574,628, and JP-A-54-1019. (A) organic thioethers described in JP-A Nos. 54-158917, etc., and (b) thioureas described in JP-A Nos. 53-82408, 55-77737, 55-2982, etc. Derivatives, (c) silver halide solvents having a thiocarbonyl group sandwiched between oxygen or sulfur atoms and nitrogen atoms, as described in JP-A-53-144319, and JP-A-54-100717 (D) imidazoles, (e) sulfite, (f) ammonia, (g) thiocyanate and the like. Particularly preferred silver halide solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the silver halide solvent used varies depending on the type. For example, in the case of thiocyanate, the preferred amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide. Regardless of which solvent is used, it is basically possible to remove the solvent by providing a water washing step after forming the first shell as described above.

  The dislocation lines of the tabular grains used in the present invention are introduced by providing a high silver iodide-containing phase inside the grains.

  The high silver iodide phase is a silver halide solid solution containing silver iodide. In this case, the silver halide is preferably silver iodide, silver iodobromide or silver chloroiodobromide. Alternatively, silver iodobromide is more preferable, and silver iodide is particularly preferable.

  The amount of silver halide forming the high silver iodide phase is preferably 30 mol% or less, more preferably 10 mol% or less of the total silver amount in terms of silver amount. The phase grown outside the high silver iodide phase needs to be lower than the silver iodide content of the high silver iodide phase, and the preferred silver iodide content is 0-12 mol%, more preferably 0-6. %, Most preferably 0 to 3 mol%.

  As a preferred method for forming the high silver iodide phase, there is a method of adding silver iodobromide or an emulsion containing silver iodide fine grains (hereinafter also referred to as “silver iodide fine grain emulsion”). As these fine particles, fine particles prepared in advance can be used, and more preferably, fine particles immediately after preparation can be used.

  First, the case of using fine particles prepared in advance will be described. In this case, there is a method in which fine particles prepared in advance are added, ripened and dissolved. As a more preferable method, there is a method in which a silver iodide fine grain emulsion is added, and thereafter an aqueous silver nitrate solution, or an aqueous silver nitrate solution and an aqueous halogen solution are added. In this case, dissolution of the fine grains contained in the silver iodide fine grain emulsion is promoted by the addition of an aqueous silver nitrate solution. The silver iodide fine grain emulsion is preferably added rapidly.

  The addition amount of the silver iodide fine grain emulsion is preferably 0.5 to 10.0%, particularly preferably 1.0 to 2.5%, based on the molar amount of all silver nitrate.

  The rapid addition of the silver iodide fine grain emulsion means that the necessary all silver iodide fine grain emulsion is added within 10 minutes. More preferably, it means adding within 7 minutes. This condition may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence / absence, type and concentration of silver halide solvent, but as described above, shorter one is preferable. When adding, it is preferable not to add an aqueous silver salt solution such as silver nitrate. The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

The composition of the fine grains contained in the silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. 100% silver iodide is preferred. Silver iodide may have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion is preferably used after a normal water washing step. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. There are no particular restrictions on the type, concentration, presence or absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin, but the grain size is 0.1 μm or less, more preferably 0.07 μm. The following is convenient for the present invention. The particle shape cannot be completely specified because it is a fine particle, but the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when it is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the fine particles are directly determined by placing the fine particles on a mesh for observation with an electron microscope and observing the fine particles with a transmission method instead of the carbon replica method. This is because the measurement error increases in the observation by the carbon replica method because the particle size is small. The particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined by using the circle diameter with the same projected area. The most effective fine particles in the present invention have a particle size of 0.06 μm or less and 0.02 μm or more, and a variation coefficient of particle size distribution of 18% or less.

  The silver iodide fine grain emulsion is preferably subjected to usual water washing described in US Pat. No. 2,614,929 after the above-described grain formation, and the concentration of protective colloid agent such as pH, pI, gelatin and the like containing iodine. The silver halide concentration is adjusted. The pH is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide is minimized or a pI value higher than that value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. In some cases, it is convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of silver in terms of silver atom per kg of the emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to be a value suitable for rapidly adding a silver iodide fine grain emulsion.

  The silver iodide fine grain emulsion is usually dissolved before being added, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of bubbles during stirring. Specifically, antifoaming agents described in Examples of US Pat. No. 5,275,929 are used. In the case of using the fine particles immediately after preparation, details of the mixer for forming silver halide fine particles can be referred to the description in JP-A-10-43570.

  The silver halide grains of the present invention preferably have a coefficient of variation of the silver iodide content distribution between grains of 20% or less. More preferably, it is 15% or less, and particularly preferably 10% or less. If the coefficient of variation is greater than 20%, the sensitivity decreases when pressure is applied, which is not preferable. The silver iodide content of individual grains can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The variation coefficient of the distribution of silver iodide content between grains is the silver iodide content when the silver iodide content of at least 100, more preferably 200, particularly preferably 300 or more emulsion grains is measured. Is a value defined by a relational expression (standard deviation / average silver iodide content) × 100 = variation coefficient. The measurement of the silver iodide content of individual grains is described, for example, in EP 147,868. There may or may not be a correlation between the silver iodide content Yi (mol%) of each grain and the sphere equivalent diameter Xi (μm) of each grain, but it is desirable that there is no correlation.

  The silver halide emulsion of the present invention is preferably provided with a hole trapping zone in at least a part of the inside of the silver halide grains. The hole capture zone in the present invention refers to a region having a function of capturing so-called holes, for example, holes generated in pairs with photoelectrons generated by photoexcitation. In the present invention, such a hole trapping zone is defined as a zone provided by intentional reduction sensitization.

  Intentional reduction sensitization in the present invention means an operation of introducing hole-capturing silver nuclei into a part or all of silver halide grains by adding a reduction sensitizer. The hole-capturing silver nucleus means a small silver nucleus having a low development activity, and this silver nucleus can prevent recombination loss during the photosensitive process and increase the sensitivity.

Known reduction sensitizers include stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds. In the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As a reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide is appropriate. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during particle growth.

  In the present invention, hole-capturing silver nuclei are preferably formed by adding a reduction sensitizer after completion of nucleation and physical ripening and immediately before starting grain growth. However, it is also possible to add a reduction sensitizer after the end of grain formation and introduce hole-capturing silver nuclei onto the grain surface.

  When a reduction sensitizer is added at the time of grain formation, some of the formed silver nuclei can remain inside the grain, but part of the silver nucleation oozes to form silver nuclei on the grain surface. In the present invention, this exuded silver nucleus can also be used as a hole-capturing silver nucleus.

  In the present invention, the intentional reduction sensitization in the process of grain formation for forming hole-capturing silver nuclei inside the silver halide grains is performed by the general formula (I-1) or the general formula (I -2) is preferably performed in the presence of the compound.

Here, the step after the final desalting is not included in the step in the course of particle formation. For example, by adding a silver salt aqueous solution, fine grain silver halide or the like in a chemical sensitization step or the like, the step of resulting silver halide grain growth is eliminated.

In the general formulas (I-1) and (I-2), W ₅₁ and W ₅₂ each independently represent a sulfo group or a hydrogen atom. However, at least one of W ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific examples of preferred compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-6,7-di And sulfonaphthalene potassium salt. The preferred addition amount may vary depending on the temperature of the system to be added, pBr and pH, the type and concentration of a protective colloid agent such as gelatin, the presence or absence, type and concentration of a silver halide solvent, but generally 1 mol of silver halide. 0.0005 mol to 0.5 mol per mol, more preferably 0.003 mol to 0.02 mol is used.

In the silver halide emulsion of the present invention, an oxidizing agent for silver can be used during the preparation process. The oxidizing agent refers to a compound having an action of acting on metallic silver and converting it into silver ions. In particular, a compound that converts very fine silver particles by-produced in the process of forming silver halide grains and chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of inorganic oxidizing agents include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H ₂ O _{2 , 2Na 2 SO 4 · H 2} O 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g. , K ₂ [Ti (O ₂₎ C ₂ O] _{· 3H 2 O, 4K 2 SO} 4 · Ti (O 2) OH · SO 4 · 2H 2 O, Na 3 _{[VO (O 2) (C 2} H 4 ₂ · 6H ₂ O], permanganate (eg KMnOK ₄ ), chromate (eg K ₂ Cr ₂ O ₇ ) and other oxyacid salts, iodine and bromine and other halogen elements and perhalogenates (For example, potassium periodate), high-valent metal salts (for example, potassium hexacyanoferrate), thiosulfonates, etc. A.

  Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, chloramine B). ) As an example.

  Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adduct, halogen elements, thiosulfonates as inorganic oxides, and quinones as organic oxidizing agents. Particularly preferred are thiosulfonates as described in JP-A-2-191938.

The timing of adding the oxidizing agent to the silver can be any time before the start of the intentional reduction sensitization, during the reduction sensitization, immediately before or after the end of the reduction sensitization, and added in several times. Also good. The addition amount varies depending on the type of oxidizing agent, but an addition amount of 1 × 10 ⁻⁷ to 1 × 10 ⁻³ per mole of silver halide is preferable.

  It is advantageous to use gelatin as the protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers. However, other hydrophilic colloids can be used.

  For example, gelatin derivatives, graft polymers of gelatin and other polymers; proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic properties, such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, homopolymers or copolymers such as polyvinyl pyrazole; A polymer material can be used.

  Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull. Soc. Sci. Photo. Japan. No. 16. An enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.

  The emulsion of the present invention is preferably washed with water for desalting and made into a protective colloid dispersion using a newly prepared protective colloid dispersion. The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is the range of 3-8. Although pAg at the time of washing can also be selected according to the purpose, it is preferably selected from 5 to 10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. The coagulation sedimentation method can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like.

When preparing the emulsion of the present invention (for example, at the time of grain formation, desalting step, chemical sensitization, before coating), it is preferable that a salt of a metal ion is present depending on the purpose. When the particles are doped, it is preferably added at the time of forming the particles, or after the formation of the particles and before the completion of the chemical sensitization when used as a particle surface modification or chemical sensitizer. In addition to the method of doping the whole grain, a method of doping only the core part or the shell part of the grain can also be selected. Examples of the dopant include Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, and Pt. Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. Any of these metals may be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. it can. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₂ IrCl ₆ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) _{4 [Fe (CN) 6],} K 3 IrCl 6, (NH 4) 3 RhCl 6, K 4 Ru (CN) 6 and the like. The ligand of the complex salt can be selected from halo, aqua, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. Although only one kind of these metal compounds may be used, two or more kinds may be used in combination.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous hydrogen halide solution (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound may be added to the reaction vessel before particle formation, or may be added during particle formation. It can also be added to an aqueous solution of a water-soluble silver salt (for example, AgNO ₃ ) or an alkali halide (for example, NaCl, KBr, K) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

  A method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to the S, Se, and Te compounds, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

  In the case of silver halide grains used in the present invention, at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization is applied to silver halide photographs. It can be applied in any step of the emulsion production process. It is preferable to combine two or more sensitization methods.

  Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose.

One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, McMillan, 1977, (TH James, The Theory of the Photographic Process, 4th ed, McCillan, 1977) pages 67-76. Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1, As described in each specification of 315,755, sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a plurality of these sensitizers at a pAg of 5-10, a pH of 5-8, and a temperature of 30-80 ° C. This can be done using a combination. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium auric thiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

The preferred amount of the gold sensitizer used in the emulsion of the present invention is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ^{−. 7} moles. A preferred range for the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ mole per mole of silver halide. A preferable range of the thiocyan compound or selenocyan compound is 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol per mol of silver halide.

  As sulfur sensitizers, described in hypo, thiourea compounds, rhodanine compounds and U.S. Pat. Nos. 3,857,711, 4,266,018, and 4,054,457. The sulfur-containing compounds that have been used can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, and 3,554,757, and JP-A-58-126526. And the above-mentioned “Photo Emulsion Chemistry” by Duffin, pages 138 to 143.

The preferred amount of sulfur sensitizer used in the present invention is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol. It is.

  A preferred sensitizing method for the emulsion of the present invention is selenium sensitization. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. Usually, unstable selenium compounds and / or non-labile selenium compounds are used by adding them and stirring the emulsion for a certain period of time at a high temperature (preferably 40 ° C. or higher). As the unstable selenium compound, compounds described in JP-B Nos. 44-15748, 43-13489, JP-A-4-25832, JP-A-4-109240, and the like are preferably used.

  Specific examples of unstable selenium sensitizers include, for example, isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium can give.

  Although preferred types of labile selenium compounds have been described above, these are not limiting. Stable selenium compounds as sensitizers in photographic emulsions are not critical as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule carries selenium and It is generally understood by those skilled in the art that it has no role other than being present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used.

  As the non-labile selenium compound used in the present invention, compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 are used. Non-labile selenium compounds include, for example, selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones. 2-selenooxazolidinethione and derivatives thereof.

  These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the selenium sensitizers can be used in combination. The combined use of labile selenium compounds and non-labile selenium compounds is preferred.

The amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of the silver halide, the ripening temperature and time, etc., but preferably the silver halide 1 It is 1 × 10 ⁻⁸ mol or more per mol. More preferably, it is 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 40 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, with respect to pH, the effects of the present invention can be obtained in a wide range from 4 to 9.

Selenium sensitization is preferably used in combination with sulfur sensitization or noble metal sensitization or both. In the present invention, thiocyanate is preferably added to the silver halide emulsion during chemical sensitization. As thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate or the like is used. Usually, it is dissolved in an aqueous solution or a water-soluble solvent and added. The addition amount is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, more preferably 5 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol, per mol of silver halide.

  The silver halide emulsion of the present invention preferably contains an appropriate amount of calcium ions and / or magnesium ions. As a result, the graininess is improved and the image quality is improved, and the storability is also improved. The appropriate range is 400 to 2500 ppm for calcium and / or 50 to 2500 ppm for magnesium, more preferably 500 to 2000 ppm for calcium and 200 to 2000 ppm for magnesium. Here, 400 to 2500 ppm of calcium and / or 50 to 2500 ppm of magnesium means that at least one of calcium and magnesium is at a concentration within a specified range. If the calcium or magnesium content is higher than these values, the inorganic salt previously retained by the calcium salt, magnesium salt, gelatin or the like is precipitated, which is not preferable because it causes failure during the production of the photosensitive material. Here, the content of calcium or magnesium is expressed by the mass converted to calcium atom or magnesium atom for all compounds containing calcium or magnesium such as calcium ion, magnesium ion, calcium salt, magnesium salt, etc. It is expressed as a concentration per unit mass.

  The calcium content in the silver halide tabular emulsion of the present invention is preferably adjusted by adding a calcium salt during chemical sensitization. Gelatin generally used at the time of emulsion production already contains 100 to 4000 ppm of calcium as solid gelatin, and may be adjusted by adding a calcium salt thereto, and if necessary, the gelatin may be washed with water or ionized. After desalting (decalcification) according to a known method such as an exchange method, the content can be adjusted with a calcium salt. As the calcium salt, calcium nitrate and calcium chloride are preferable, and calcium nitrate is most preferable. Similarly, the magnesium content can be adjusted by adding a magnesium salt during the production of the emulsion. As the magnesium salt, magnesium nitrate, magnesium sulfate and magnesium chloride are preferable, and magnesium nitrate is most preferable. The quantitative method of calcium or magnesium can be determined by ICP emission spectroscopic analysis. Calcium and magnesium may be used alone or in combination. More preferably, it contains calcium. Calcium or magnesium can be added at any time during the silver halide emulsion production process, but it is preferably after grain formation until immediately after spectral sensitization or chemical sensitization, and after sensitizing dye addition. Is more preferable. Further, it is particularly preferable to add after the addition of the sensitizing dye and before the chemical sensitization.

  As a particularly useful compound for the purpose of reducing the fog of the silver halide emulsion and suppressing the fog increase during storage, a mercaptotetrazole compound having a water-soluble group described in JP-A-4-16838 can be mentioned. Further, the above-mentioned published patent publication discloses that storage stability is improved by using a combination of a mercaptotetrazole compound and a mercaptothiadiazole compound.

  The emulsion used in the present invention may be chemically sensitized at the surface or at any position from the surface, but it is preferable to chemically sensitize the surface. In the case of chemically sensitizing the inside, the method described in JP-A-63-264740 can be referred to.

  The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Thiazoles (e.g., benzothiazolium salts); nitroimidazoles; nitrobenzimidazoles; chlorobenzimidazoles; bromobenzimidazoles; mercaptothiazoles; mercaptobenzothiazoles; mercaptobenzimidazoles; Benzotriazoles; nitrobenzotriazoles; mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; For example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene It can be added a number of compounds known as antifoggants or stabilizers, such as classes. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control grain habit, reduce grain size, decrease grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

  The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

  In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, A 5-6 membered heterocyclic nucleus of a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Laid-Open Nos. 52-110618, and 52-109925. Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization.

The timing of adding the sensitizing dye to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it occurs at the time after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666. Spectral sensitization can be performed simultaneously with chemical sensitization by adding at the same time as the sensitizer, or can be performed prior to chemical sensitization as described in JP-A No. 58-113928. Spectral sensitization can be started by adding before the completion of silver halide grain precipitation. Furthermore, adding these compounds separately as taught in U.S. Pat. No. 4,225,666, ie adding some of these compounds prior to chemical sensitization and the balance Can be added after chemical sensitization, and any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

The silver halide grains other than the tabular grains used in the light-sensitive material of the present invention are described below.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing about 1 mol% to about 10 mol% of silver iodide.

  Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons and tetradecahedrons, grains having regular crystals such as spheres and plates, twin planes, etc. Those having crystal defects of the above or a composite form thereof may be used. The silver halide grains may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm. The emulsion may be a polydisperse emulsion or a monodisperse emulsion.

  The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) No. 17643 (December 1978), pages 22-23, “I. Emulsion preparation and types”, and 18716 (November 1979), page 648, ibid. 307105 (November 1989), 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemie et Phisique Photographe, Paul Montel, 1967), "Photoemulsion Chemistry". Published by Focal Press (GF Duffin, Photographic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photoemulsions" by Zelikman et al., Published by Focal Press (V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964).

  Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred. The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, may have a layered structure, or silver halides having different compositions may be joined by epitaxial joining. Alternatively, for example, it may be bonded to a compound other than silver halide such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.

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

  Silver halide grains with fogged grain surfaces as described in US Pat. No. 4,082,553, grain interiors as described in US Pat. No. 4,626,498 and JP-A-59-214852 The fogged silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The silver halide emulsion in which the inside or the surface of the grain is fogged means a silver halide grain which can be developed uniformly (non-imagewise) regardless of the unexposed part and the exposed part of the photosensitive material. . A method for preparing silver halide grains fogged inside or on the surface is described in US Pat. No. 4,626,498 and JP-A-59-214852.

  The silver halide forming the inner nucleus of the core / shell type silver halide grain in which the inside of the grain is fogged may have the same halogen composition or a different halogen composition. Any silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. There is no particular limitation on the grain size of these fogged silver halide grains, but 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited, and may be regular grains. The emulsion may be a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain mass or grain number has an average grain size). Those having a particle size within ± 40%) are preferred.

  In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

  In the method for producing a photographic light-sensitive material of the present invention, a photographic useful substance is usually added to a photographic coating solution, that is, added to a hydrophilic colloid solution. The various techniques and inorganic / organic materials that can be used in the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same are generally described in Research Disclosure No. 308119 (1989) and the same. 37038 (1995) and 40145 (1997) can be used.

  In addition to this, more specifically, for example, the technology and inorganic / organic materials that can be used in the color photographic light-sensitive material to which the silver halide photographic emulsion of the present invention can be applied are described in European Patent No. 436,938A2. In the following sections of the document and in the patent specifications cited below.

Item Location 1) Layer structure Page 146, line 34 to page 147, line 25 2) Can be used together Page 147, line 26 to page 148, line 12, silver halide emulsion 3) Can be used together From page 137, line 35 to page 146, line 33, page 14
Yellow coupler, page 9, lines 21 to 23 4) can be used together page 149, lines 24 to 28; European Patent 42
Magenta coupler 1,453A1 page 3 line 5 to page 25 line 55
Eye 5) Can be used together, page 149, lines 29-33; European Patent 432
Cyan coupler, 804A2, page 3, line 28 to page 40, line 2 6) polymer coupler, page 149, lines 34 to 38; European Patent 435
, 334A2 page 113 line 39 to page 123
37th line 7) Colored coupler, page 53, line 42 to page 137, line 34, page 149
Page 39 line 45 line 8) can be used together page 7 line 1 to page 53 line 41 line 149 page 46
Functional couplers line to page 150, line 3; European Patent No. 435,33
4A2 page 3 line 1 to page 29 line 50 line 9) antiseptic / antifungal page 150 line 25 to line 28
10) Formalin, page 149, lines 15 to 17 Scavenger
11) Can be used together, page 153, lines 38-47; European Patent 421
Other additives, 453A1, page 75, line 21 to page 84, 56
Line, page 27, line 40 to page 37, line 40
12) Distribution method Page 150, lines 4-24
13) Support body, page 150, lines 32 to 34
14) Film thickness and film properties, page 150, lines 35-49
15) Color development process, page 150, line 50 to page 151, line 47
16) Desilvering process, page 151, line 48 to page 152, line 53
17) Automatic processor Page 152, line 54 to page 153, line 2
18) Water washing / stabilization process, page 153, lines 3 to 37.

  The photosensitive material of the present invention can also be applied to a photosensitive material having a transparent magnetic recording layer. Regarding the transparent magnetic recording layer and the accompanying material technology, and the photosensitive material used in the advanced photo system, the processing method thereof, and the utilization method after the processing, column 18 of US Pat. No. 6,220,744 is disclosed. , Line 39 to column 23, line 45 are described in detail.

  The silver halide color photographic light-sensitive material of the present invention is a color reversal photographic light-sensitive material on the premise that it is processed by color reversal processing including steps of performing black-and-white development, reversal processing, and color development.

  Hereinafter, the overall color reversal process of the present invention will be described. First, black and white development (first development), which is the first step, will be described.

A conventionally known developing agent can be used for the black and white developer. Developing agents include dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), amino Phenols (for example, N-methyl-p-aminophenol, N-methyl-3-methyl-p-aminophenol), ascorbic acid and its isomers and derivatives can be used alone or in combination. Preferred developing agents are potassium hydroquinone monosulfonate or sodium hydroquinone monosulfonate. The addition amount of these developing agents is about 1 × 10 ^{−5 to 2} mol / L per liter of the developing solution.

  If necessary, a preservative can be used in the black and white developer of the present invention. As preservatives, sulfites and bisulfites are generally used. The amount of these added is 0.01 to 1 mol / L, preferably 0.1 to 0.5 mol / L. Moreover, ascorbic acid is also an effective preservative, and the preferable addition amount is 0.01 mol / L to 0.5 mol / L. In addition, hydroxylamines, saccharides, o-hydroxy ketones, hydrazines and the like described in general formula (I) of JP-A-3-144446 can also be used. In this case, the amount added is 0.1 mol / L or less.

  The pH of the black and white developer of the present invention is preferably 8 to 12, and most preferably 9 to 11. Various buffering agents can be used to maintain the pH. Preferred buffering agents are carbonate, phosphate, borate, 5-sulfosalicylate, hydroxybenzoate, glycine salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3, Examples thereof include 4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, valine salt, lysine salt and the like. In particular, the use of carbonates, borates, and 5-sulfosalicylates is preferable in terms of keeping the pH range and being inexpensive. These buffering agents may be used alone or in combination of two or more. Further, an acid and / or alkali may be added to obtain the target pH.

  As the acid, an inorganic or organic water-soluble acid can be used. For example, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, propionic acid, ascorbic acid and the like. Moreover, various hydroxides and ammonium salts can be added as the alkali. For example, potassium hydroxide, sodium hydroxide, ammonia water, triethanolamine, diethanolamine and the like can be mentioned.

  The black-and-white developer used in the present invention preferably contains a silver halide solvent as a development accelerator. For example, thiocyanate, sulfite, thiosulfate, 2-methylimidazole, and thioether compounds described in JP-A-57-63580 are preferable. The amount of these compounds added is preferably about 0.005 to 0.5 mol / L.

  Other development accelerators include various quaternary amines, polyethylene oxides, 1-phenyl-3-pyrazolidones, primary amines, N, N, N ′, N′-tetramethyl-p-phenylenediamine and the like. be able to.

  The black-and-white developer used in the present invention contains diethylene glycol, propylene glycol, other polyethylene glycols, amines such as diethanolamine and triethanolamine as solubilizing agents, quaternary ammonium salts as sensitizers, and various interfaces. Activators and hardeners can be used.

  Various anti-fogging agents may be added to the black and white development process of the present invention for the purpose of preventing development fog. Antifoggants are preferably alkali metal halides such as sodium chloride, potassium chloride, potassium bromide, sodium bromide and potassium iodide, and organic antifoggants. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and thiosalicylic acid Such mercapto-substituted aromatic compounds can be used. These antifoggants include those that elute from the color reversal photosensitive material during processing and accumulate in these developing solutions.

Among these, the addition concentration of iodide is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol / L. Bromide is also preferred for preventing fogging, and the preferred concentration is about 0.001 mol / L to 0.1 mol / L, and more preferably about 0.01 to 0.05 mol / L.

  Furthermore, the black-and-white developer of the present invention may contain a swelling inhibitor (for example, an inorganic salt such as sodium sulfate or potassium sulfate) or a hard water softener. As the water softening agent, those having various structures such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic inorganic phosphonic acid can be used. Specific examples are shown below, but are not limited thereto.

  Ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′ N′-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid. Two or more of these hard water softeners may be used in combination. A preferable addition amount is 0.1 g to 20 g / L, and more preferably 0.5 g to 10 g / L.

The standard processing time for black-and-white development is 6 minutes, and an increase / decrease processing can be performed by appropriately changing the processing time. Usually, the processing time is changed between 2 minutes and 18 minutes. The treatment temperature is 20 ° C to 50 ° C, preferably 33 ° C to 45 ° C. The replenishment amount of the black and white developer is about 100 mL to 5000 mL, preferably about 200 mL to 2500 mL per 1 m ² of the photosensitive material.

In the processing of the present invention, after black-and-white development, washing and / or rinsing treatment is performed as necessary, followed by processing in a reversal processing step, followed by color development processing. The washing or rinsing bath may be one bath, but it is more preferable to employ a multistage countercurrent system with two or more tanks for the purpose of reducing the replenishment amount. Here, rinsing is a method in which a relatively large amount of water is replenished, whereas rinsing is a method in which the replenishment amount is reduced to other treatment bath levels. The replenishing amount of washing water is preferably about 3 L to ²⁰ L per 1 m ² of the photosensitive material. Moreover, the replenishment amount of the rinse bath is 50 mL to 2 L, more preferably about 100 mL to 500 mL, and the amount of water used is greatly reduced as compared with the water washing step. Moreover, an oxidizing agent, a chelating agent, a buffering agent, a bactericidal agent, a fluorescent brightening agent, etc. can be added to the rinsing bath of the present invention as required.

  Subsequently, the reversal bath or light fogging process is entered. In the reversal bath, a fogging agent known as a chemical fogging agent, that is, stannous ion-organic phosphate complex (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex (specialized) No. 56-32616), stannous ion complex salts such as stannous ion-aminopolycarboxylic acid complex salts (US Pat. No. 1,209,050), and general formula (II) of JP-A-11-109573. Or a stannous ion complex salt of a chelating agent represented by formula (III), a borohydride compound (US Pat. No. 2,984,567), a heterocyclic amine borane compound (UK Patent 1,011,000) Boron compounds, etc. are used. The pH of the reversal bath ranges over a wide range from the acidic side to the alkaline side depending on the kind of the fogging agent, and is in the range of pH 2 to 12, most of 2.5 to 10, particularly 3 to 9.

The concentration of tin (II) ions in the reversal bath is 1 × 10 ^{−3 to} 5 × 10 ⁻² mol / L, preferably 2 × 10 ^{−3 to} 1.5 × 10 ⁻² mol / L. Further, the reversal bath preferably contains propionic acid, acetic acid, or an alkylene dicarboxylic acid compound described in the general formula (I) of JP-A No. 11-109572 in order to enhance the solubility of the tin (II) chelate. . Furthermore, it is preferable to contain a sorbate and a quaternary ammonium compound described in US Pat. No. 5,811,225 as a fungicide.

The time for the reversal bath is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes, and more preferably 30 seconds to 90 seconds. The temperature of the reversal bath is preferably one of the first development, the subsequent rinsing or washing with water and the color development, or the temperature range of each of these baths, and is generally 20 to 50 ° C, preferably 33 to 45 ° C. The replenishment amount of the reversal bath is 10 to 2000 mL, preferably 200 to 1500 mL per 1 m ² of the light-sensitive material.

  The tin (II) chelate in the reversal bath is effective over a wide pH range, so it is not necessary to add a pH buffering agent. However, organic acids such as citric acid and malic acid, boric acid, sulfuric acid, hydrochloric acid, etc. Addition of acids, alkalis and salts for imparting pH buffering properties such as inorganic acids, alkali carbonates, caustic alkalis, borax and potassium metaborate is not prevented. Further, if necessary, a water softener such as aminopolycarboxylic acid, a swelling inhibitor such as sodium sulfate, and an antioxidant such as p-aminophenol may be added.

  After processing in the reversal bath, the color development process is started. The color developer used in the color development processing of the present invention is an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, a p-phenylenediamine compound is preferably used. Representative examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, and 3-methyl-4. -Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p -Toluenesulfonate, tetraphenylborate, p- (t-octyl) benzenesulfonate and the like. These developing agents may be used in combination of two or more if necessary. A preferable addition amount is about 0.005 mol / L to 0.1 mol / L, preferably about 0.01 mol / L to 0.05 mol / L.

  The pH of the color developer of the present invention is preferably in the range of 8 to 13, more preferably 10.0 to 12.5, and particularly preferably 11.5 to 12.3. Various buffers are used to maintain this pH.

  Examples of the buffering agent having a buffer region at pH 8.0 or more used in the present invention include carbonate, phosphate, borate, 5-sulfosalicylate, tetraborate, hydroxybenzoate, glycine salt, N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, Proline salts, trishydroxyaminomethane salts, lysine salts, and the like can be used. In particular, carbonates, phosphates, and 5-sulfosalicylates are excellent in solubility and buffering ability in a high pH range of pH 10.0 or higher, and adversely affect photographic performance even when added to a color developer (such as stains). It is particularly preferable to use these buffering agents.

  Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and dipotassium 5-sulfosalicylate. , Sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2-hydroxybenzoic acid Examples thereof include sodium (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and preferably trisodium phosphate, tripotassium phosphate, disodium phosphate, Dipotassium phosphate, dipotassium 5-sulfosalicylate Beam, 5-sulfosalicylic acid disodium. These buffering agents may be added to the developer alone or in combination of two or more, and can be adjusted to the target pH with an alkali agent or acid.

  The amount of the buffer added to the color developer is preferably 0.1 mol / L or more (in the case of combined use), particularly 0.1 mol / L to 0.4 mol / L. It is particularly preferred.

  In the present invention, various development accelerators may be used in combination as necessary. Examples of development accelerators include various pyridinium compounds represented by the specifications of US Pat. No. 2,648,604, Japanese Patent Publication No. 44-9503, and US Pat. No. 3,171,247, and other cationic resins. Compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, Japanese Examined Patent Publication No. 44-9304, US Pat. Nos. 2,533,990, 2,531,832, and 2 , 950, 970, 2,577, 127, polyethylene glycol and derivatives thereof, nonionic compounds such as polythioethers, U.S. Pat. No. 3,201,242 A thioether compound may be used.

  Further, benzyl alcohol or its solvent, diethylene glycol, triethanolamine, diethanolamine or the like can be used as necessary. However, considering the environmental load, the solubility of the liquid, the generation of tar, etc., it is preferable to use these as little as possible.

  Moreover, the same silver halide solvent as a black-and-white developing solution can also be contained. Examples thereof include thiocyanate, 2-methylimidazole, and thioether compounds described in JP-A-57-63580. Particularly preferred is 3,6-dithiaoctane-1,8-diol.

  In the color development process of the present invention, it is not necessary to prevent development fogging, but when running while replenishing the color film, various antifogging agents are added for the purpose of maintaining the stability of the composition and performance of the liquid. Also good. As the antifoggant in these development steps, alkali metal halides such as potassium chloride, sodium chloride, potassium bromide, sodium bromide and potassium iodide and organic antifoggants are preferred. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and thiosalicylic acid Such mercapto-substituted aromatic compounds can be used. These antifoggants include those that elute from the color reversal photosensitive material during processing and accumulate in these developing solutions.

  Various preservatives can be used in the color developer according to the present invention. As typical preservatives, hydroxylamines and sulfites can be used, and sulfites are preferred. These addition amounts are about 0-0.1 mol / L.

  The color developer used in the present invention may contain an organic preservative in place of the hydroxylamine or sulfite ion. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent when added to the processing solution of the color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of the color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Ketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. are particularly effective. Preservative. These are JP-B-48-30696, JP-A-52-143020, JP-A-63-4235, JP-A-63-30845, JP-A-63-21647, JP-A-63-44655, JP-A-63-53551, JP-A-63. No. -43140, No. 63-56654, No. 63-58346, No. 63-43138, No. 63-146041, No. 63-44657, No. 63-44656, US Pat. No. 3,615,503, No. 2,494,903, JP-A-1-97953, 1-186939, 1-186940, 1-187557, 2-306244, etc. . As other preservatives, various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, JP-A-63-239447, Amines such as those described in JP-A-63-128340, JP-A-1-186939 and 1-187557, alkanolamines described in JP-A-54-3532, Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be used as necessary. Particularly alkanolamines such as triethanolamine, dialkylhydroxylamines such as N, N-diethylhydroxylamine and N, N-di (sulfoethyl) hydroxylamine, and hydrazines such as N, N-bis (carboxymethyl) hydrazine Derivatives (excluding hydrazine) or aromatic polyhydroxy compounds typified by sodium catechol-3,5-disulfonate are preferred.

  The amount of these organic preservatives added is preferably about 0.02 mol / L to 0.5 mol / L, more preferably about 0.05 mol / L to 0.2 mol / L, and 2 if necessary. More than one species may be used in combination.

  In addition, the color developer according to the present invention includes organic solvents such as diethylene glycol and triethylene glycol; dye-forming couplers; competitive couplers such as citrazic acid, J acid, and H acid; nucleating agents such as sodium boron hydride; Auxiliary developer such as 1-phenyl-3-pyrazolidone; viscosity imparting agent; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriamine Pentaacetic acid, triethylenetetramine hexaacetic acid, aminopolycarboxylic acid represented by compounds described in JP-A-58-195845, 1-hydroxyethylidene-1,1′-diphosphonic acid, Research Disclosure No. 18170 (1 And organic phosphonic acids, aminotris (methylenephosphonic acid), ethylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid and the like described in May 1997), JP-A 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, 55-126241, 55-65955, 55-65956, and Research Disclosure No. A chelating agent such as phosphonocarboxylic acid described in No. 18170 (May 1979) can be contained. The amount of these chelating agents added is 0.05 g / L to 20 g / L, preferably about 0.1 g to 5 g / L, and if necessary, two or more kinds may be used in combination. Moreover, you may add various surfactants, such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid polyalkyleneimine as needed.

The processing temperature of the color developer that can be applied to the present invention is preferably 20 to 50 ° C, more preferably 33 to 45 ° C. The treatment time is preferably 20 seconds to 10 minutes, more preferably 2 minutes to 6 minutes. The replenishing amount is preferably as small as possible so that the activity can be maintained, but it is suitably 100 to 3000 mL, preferably 400 to 2200 mL per 1 m ^{2 of} the light-sensitive material.

The color reversal photosensitive material that has undergone color development is then desilvered. The desilvering process is usually performed by the following process.
1. (Color development)-Adjustment-Bleaching-Fixing (Color development) -Washing-Bleaching-Fixing (Color development)-Bleaching-Fixing 4. (Color development) -washing-bleaching-washing-fixing (Color development) -Bleaching-Washing-fixing (Color development) -Washing-Bleaching and fixing7. (Color development)-Adjustment-Bleach fixing 8. (Color development)-Bleach fixing 9. (Color development)-Washing-Bleaching-Bleach fixing 10. (Color development)-Bleaching-Bleach fixing 11. (Color development) -Washing-Bleaching-Bleaching-fixing-Fixing Among the above steps, 1, 2, 3, 7 are preferred.

  The replenishing method in the above processing step may replenish the replenisher of each bath individually to the corresponding processing bath, as in the prior art. The bleach-fixing bath may be supplemented with only the fixer composition. In step 11, the overflow solution of the bleaching solution is introduced into the bleach-fixing solution, the overflow solution of the fixing solution is introduced into the bleach-fixing solution in a countercurrent manner, and both are overflowed from the bleach-fixing bath. May be.

The most commonly used bleaching agent for the bleaching bath or bleach-fixing bath of the present invention is an aminopolycarboxylic acid iron (III) complex salt. As representative examples of these aminopolycarboxylic acids and salts thereof,
A-1 Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid diammonium salt A-4 Diethylenetriaminepentaacetic acid A-5 Cyclohexanediamine tetraacetic acid A-6 Cyclohexanediamine tetraacetic acid disodium salt A-7 Iminodiacetic acid A-8 1,3-diaminopropanetetraacetic acid A-9 Methyliminodiacetic acid A-10 Hydroxyethyliminodiacetic acid A-11 Glycol ether diamine tetraacetic acid A-12 Ethylenediaminetetrapropionic acid A-13 N- (2-carboxyl Ethyl) -iminodiacetic acid A-14 Ethylenediamine dipropionic acid A-15 β-alanine diacetic acid A-16 Ethylenediamine dimalonic acid A-17 Ethylenediamine disuccinic acid A-18 Propylenediamine disuccinic acid It can gel.

  The aminopolycarboxylic acid ferric complex salt may be used in the form of a complex salt, or a ferric ion complex salt may be formed in a solution using the ferric salt and aminopolycarboxylic acid. Further, one or more aminopolycarboxylic acids may be used. In either case, the aminopolycarboxylic acid may be used in excess of the ferric ion complex salt.

  The bleaching solution or bleach-fixing solution containing the ferric ion complex may contain a metal ion complex salt such as cobalt or copper other than iron.

  These bleaching agents are added in an amount of 0.02 to 0.5 mol, preferably 0.05 to 0.3 mol, per liter of a bath having bleaching ability.

  Various bleach-fixing accelerators can be added to the bleaching bath and the bleach-fixing bath of the present invention. Examples of such bleach accelerators include those described in, for example, US Pat. No. 3,893,858, British Patent 1,138,842, and JP-A-53-141623. Various mercapto compounds, compounds having a disulfide bond as described in JP-A-53-95630, thiazolidine derivatives as described in JP-B-53-9854, JP-A-53-94927 Isothiourea derivatives as described, thiourea derivatives as described in JP-B-45-8506, JP-B-49-26586, and thioamide compounds as described in JP-A-49-42349 And dithiocarbamates as described in JP-A-55-26506. Further examples of bleach accelerators include alkyl mercapto compounds that are unsubstituted or substituted with a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group (which may have a substitution such as an alkyl group or an acetoxyalkyl group), and the like. Can be used. For example, trithioglycerin, α, α′-thiodipropionic acid, δ-mercaptobutyric acid and the like can be mentioned. Furthermore, the compounds described in US Pat. No. 4,552,834 can also be used.

The amount added when a compound having a mercapto group or disulfide bond in the molecule, a thiazoline derivative or an isothiourea derivative is added to the adjusting solution or the bleaching solution is necessary for the type of photographic material to be processed, the processing temperature, and the intended processing. Although it varies depending on time and the like, 1 × 10 ⁻⁵ to 10 ⁻¹ mol per 1 L of the processing solution is appropriate, and preferably 1 × 10 ^{−4 to} 5 × 10 ⁻² mol.

  In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution used in the present invention contains a rehalogen such as bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride and ammonium chloride. An agent may be included. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. One or more kinds of inorganic acids, organic acids having a buffer capacity, organic acids, and salts thereof, which are commonly used in bleaching solutions, can be added. Further, the pH of the solution having bleaching ability is preferably 4.0 to 8.0, particularly 5.0 to 7.0 in use.

  In the bleach-fixing solution, as a fixing agent, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate, ethylenebisthioglycolic acid, 3,6-dithia These are water-soluble silver halide solubilizers such as thioether compounds such as -1,8-octanediol and thioureas, and these can be used alone or in combination. Further, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. The amount of these fixing agents is 0.1 to 3 mol, preferably 0.2 to 2 mol, per liter of the bath having fixing ability.

  When the fixing solution is used in the present invention, the fixing agent is also a known fixing agent, that is, a thisulfate such as sodium thiosulfate or ammonium thiosulfate, a thiocyanate such as sodium thiocyanate, ammonium thiocyanate or potassium thiocyanate, ethylene bis It is a water-soluble silver halide solubilizer such as thioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and thioureas, and these are used alone or in combination of two or more. be able to. The concentration of the fixing agent is 0.1 mol to 3 mol, preferably 0.2 mol to 2 mol, per liter of the fixing solution.

  In addition to the above-mentioned additives, liquids having fixing ability include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds as preservatives ( For example, acetaldehyde sodium bisulfite) can be contained. Sulfinic acids (such as benzenesulfinic acid) and ascorbic acid are also effective preservatives. Furthermore, various organic brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, antibacterial agents, antibacterial agents, and organic solvents such as methanol can be contained.

The replenishing amount of the bleaching solution, fixing solution, bleach-fixing solution and the like in the present invention can be arbitrarily set as long as the functions of the respective processing baths are satisfied, but is preferably 30 to 2000 mL per 1 m ² of the light-sensitive material. More preferably, it is 50 mL-1000 mL. The treatment temperature is preferably 20 ° C to 50 ° C, more preferably 33 ° C to 45 ° C. The treatment time is 10 seconds to 10 minutes, preferably 20 seconds to 6 minutes.

  In general, after desilvering such as fixing or bleach-fixing, washing and / or stabilization is performed. The stabilizing solution generally contains an image stabilizer, but may not contain an image stabilizer. In this case, a rinsing solution (cleaning solution) may be called to distinguish from the stabilizing solution.

  The amount of washing water in the washing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler) and application, the washing water temperature, the number of washing tanks (number of stages), and various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is the Journal of the Society of Motion Picture and Television Engineers. 64, p.248-253 (May 1955 issue). Usually, the number of stages in the multistage counter-current system is preferably 2 to 15, particularly preferably 2 to 10.

  According to the multi-stage counter-current system, the amount of water to be washed can be greatly reduced. Due to the increase in the residence time of water in the tank, there is a problem that bacteria propagate and the generated suspended matter adheres to the photosensitive material. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, chlorinated bactericides such as isothiazolone compounds and siabendazoles described in JP-A-57-8542 and chlorinated sodium isocyanurate described in JP-A-61-120125, JP-A-61-276761 Benzotriazole, copper ion, and other publications described in the gazette, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” (1986) Sankyo Publishing, Hygiene Technology Association, “Microbial Decontamination, Sterilization, Antifungal Technology” (1982) The bactericides described in the “Industrial Antibacterial and Antifungal Encyclopedia” (1986) edited by the Industrial Technology Association of Japan and the Japanese Society for Antibacterial and Antifungal Society may also be used.

  Further, in the washing water, stabilizing solution or rinsing solution, a surfactant as a draining agent and a chelating agent represented by EDTA as a hard water softener can be used. Surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkyl Naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant, and the like. Two or more species can be used in combination. In addition, a fluorine-based surfactant or a siloxane-based surfactant described in US Pat. No. 5,716,765 can also be used.

  Among the nonionic surfactants, nonionic surfactants such as alkylpolyethylene oxides, alkylphenoxypolyethylene oxides, and alkylphenoxypolyhydroxypropylene oxides are preferable, and alkyl-polyethylene oxides having 5 to 15 carbon atoms (5 ~ 12) Alcohol.

  Moreover, in order to improve the solubility of surfactant, it is also preferable to contain solubilizers of amines such as diethanolamine and triethanolamine, and glycols such as diethylene glycol and propylene glycol.

  It is preferable to add a chelating agent for collecting heavy metals to the stabilizing solution or the rinsing solution in order to improve the stability of the solution and reduce the occurrence of dirt. As the chelating agent, the same compounds as those added to the developer and the bleaching solution can be used.

  The stabilizer or rinse solution of the present invention is preferably added with an antibacterial / antifungal agent for the purpose of preventing the occurrence of fungal sputum, and commercially available products can be used. Further, a surfactant, a fluorescent brightening agent, and a hardener can be added.

  The pH of the stabilizing solution or rinsing solution and washing water of the present invention is 4-9, preferably 5-8. The treatment temperature and treatment time can also be variously set depending on the characteristics of the light-sensitive material, applications, etc., but are generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 4 minutes. Furthermore, when the stabilizer or rinsing solution of the present invention is treated directly with the stabilizing solution or the rinsing solution after the desilvering process without washing with water, the effect of preventing soiling is remarkably exhibited.

The replenishing amount of the stabilizing solution or rinsing solution of the present invention is preferably 200 to 2000 mL per 1 m ² of the sensitive material. The overflow liquid accompanying the washing with water and / or the replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process.

  In order to reduce the amount of washing water used, ion exchange or ultrafiltration may be used, and it is particularly preferable to use ultrafiltration. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but the temperature is increased to accelerate the processing and shorten the processing time, or conversely, the temperature is lowered to achieve an improvement in image quality and stability of the processing solution. be able to.

  In the processing of the light-sensitive material according to the method of the present invention, when stabilization is carried out directly without going through a water washing step, it is described in JP-A-57-8543, 58-14834, 60-220345, etc. Any known method can be used.

  In addition, it is also a preferable aspect to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, and magnesium and bismuth compounds.

  Drying is performed following the water washing and / or stabilization step. From the viewpoint of reducing the amount of moisture brought into the image film, drying can be accelerated by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a matter of course as an improvement means from the dryer side, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material or by the method of removing the exhaust air.

(Example)
(Example-1)
Hereinafter, the present invention will be specifically described by way of examples, but is not limited thereto.

Preparation of sample 101 (sensitive material of the present invention)
(i) Preparation of triacetyl cellulose film Triacetyl cellulose was dissolved in dichloromethane / methanol = 92/8 (mass ratio) by a normal solution casting method (13% by mass), and the plasticizer triphenylphosphine was used. A band method was used in which fete and biphenyldiphenyl phosphate were added at a mass ratio of 2: 1 so that the total amount was 14% with respect to triacetyl cellulose. The thickness of the support after drying was 97 μm.

(ii) Contents of undercoat layer The following undercoat was applied to both surfaces of the triacetylcellulose film. The number represents the mass contained per 1.0 L of the undercoat liquid.

Gelatin 10.0g
Salicylic acid 0.5g
Glycerin 4.0g
700 mL of acetone
Methanol 200mL
Dichloromethane 80mL
Formaldehyde 0.1mg
Add water and add 1.0L.

(iii) Application of Back Layer The following back layer was applied to one side of the support that had been primed as described above.

1st layer binder: acid-treated gelatin (isoelectric point 9.0) 1.00 g
Polymer latex: P-2 (average particle size 0.1 μm) 0.13 g
Polymer latex: P-3 (average particle size 0.2 μm) 0.23 g
UV absorber U-1 0.030g
UV absorber U-2 0.010g
UV absorber U-3 0.010g
UV absorber U-4 0.020g
High-boiling organic solvent Oil-2 0.030g
Surfactant W-2 0.010g
Surfactant W-4 3.0 mg.

Second layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.10 g
Polymer latex: P-3 (average particle size 0.2 μm) 0.11 g
UV absorber U-1 0.030g
UV absorber U-3 0.010g
UV absorber U-4 0.020g
High-boiling organic solvent Oil-2 0.030g
Surfactant W-2 0.010g
Surfactant W-4 3.0mg
Dye D-2 0.10 g
Dye D-10 0.12g
Potassium sulfate 0.25g
Calcium chloride 0.5mg
Sodium hydroxide 0.03g.

3rd layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.30 g
Surfactant W-2 0.020g
Potassium sulfate 0.30g
Sodium hydroxide 0.03g.

4th layer Binder: Lime-processed gelatin (isoelectric point 5.4) 1.15g
1: 9 copolymer of methacrylic acid and methyl methacrylate
(Average particle size 2.0μm) 0.040g
6: 4 copolymer of methacrylic acid and methyl methacrylate
(Average particle size 2.0μm) 0.030g
Surfactant W-2 0.060g
Surfactant W-1 7.0mg
Curing agent H-1 0.23 g.

(iv) Application of photosensitive emulsion layer Sample 101 was coated with the photosensitive emulsion layer shown below on the opposite side of the back layer. The number represents the amount added per m ² . The effect of the added compound is not limited to the described use.
The gelatin shown below had a molecular weight (mass average molecular weight) of 100,000 to 200,000. The content of main metal ions was 2500 to 3000 ppm calcium, 1 to 7 ppm iron, and 1500 to 3000 ppm sodium.
Gelatin having a calcium content of 1000 ppm or less was also used.

  Each layer is prepared as an emulsified dispersion containing gelatin as the organic compound to be incorporated (W-2, W-3, and W-4 are used as surfactants), and the photosensitive emulsion and yellow colloidal silver are also dispersed in gelatin. A coating solution prepared as a product and mixed to obtain the described addition amount was prepared and used for coating. Cpd-H, O, P, Q, dyes D-1,2,3,5,6,8,9,10, H-1, P-3, F-1 to 9 are water or methanol, dimethylformamide, It was dissolved in an appropriate water-miscible organic solvent such as ethanol or dimethylacetamide and added to the coating solution for each layer.

  The gelatin concentration (mass content of gelatin solid / volume of coating solution) of each layer thus adjusted is in the range of 2.5% to 15.0%, and the pH of each coating solution is 5.0 to 8.5. In the coating solution for a layer containing a silver halide emulsion, the pAg value was 7.0 to 9.5 when adjusted to pH 6.0 and a temperature of 40 ° C.

  After coating, the sample was dried by a multi-stage drying process maintained at a temperature in the range of 10 ° C to 45 ° C.

First layer: Antihalation layer Black colloidal silver 0.20g
Gelatin 2.20g
Compound Cpd-B 0.010g
UV absorber U-1 0.050g
UV absorber U-3 0.020g
UV absorber U-4 0.020g
UV absorber U-5 0.010g
UV absorber U-2 0.070g
Compound Cpd-F 0.20g
Compound Cpd-R 0.020g
Compound Cpd-S 0.020g
High-boiling organic solvent Oil-2 0.020g
High boiling point organic solvent Oil-6 0.020g
High boiling point organic solvent Oil-8 0.020g
Dye D-4 1.0mg
Dye D-8 1.0mg
0.05 g of a microcrystalline solid dispersion of dye E-1.

Second layer: Intermediate layer 0.4g gelatin
Compound Cpd-F 0.050g
High-boiling organic solvent Oil-6 0.010 g.

Third layer: Shortwave green-sensitive interimage imparting layer Emulsion R Silver amount 0.03g
Emulsion S Silver amount 0.05g
Emulsion T Silver amount 0.24g
Fine grain silver iodide (average sphere equivalent diameter 0.05μm)
0.005g silver
Gelatin 0.5g
Compound Cpd-M 0.030g
High boiling point organic solvent Oil-6 0.030g
High boiling point organic solvent Oil-7 5.0mg
Dye D-7 4.0 mg.

4th layer: Red-sensitive interimage effect imparting layer Emulsion U Silver amount 0.14g
Gelatin 0.25g
Compound Cpd-M 0.010g
High boiling point organic solvent Oil-6 0.010g
High-boiling organic solvent Oil-7 1.7 mg.

5th layer: Intermediate layer Gelatin 1.50g
Compound Cpd-M 0.10 g
Compound Cpd-F 0.030g
Compound Cpd-D 0.010g
Compound Cpd-K 3.0mg
UV absorber U-6 0.010g
High boiling point organic solvent Oil-6 0.10g
High boiling point organic solvent Oil-3 0.010g
High boiling point organic solvent Oil-4 0.010 g.

Layer 6: Low sensitivity red sensitive emulsion layer Emulsion A Silver amount 0.05g
Emulsion B Silver amount 0.40g
Emulsion C Silver amount 0.15g
Yellow colloidal silver Silver amount 0.1mg
Gelatin 0.60g
Coupler C-1 0.11g
Coupler C-2 7.0mg
UV absorber U-2 3.0mg
Compound Cpd-D 1.0mg
Compound Cpd-J 2.0mg
High boiling point organic solvent Oil-5 0.050g
High boiling point organic solvent Oil-10 0.010 g.

Layer 7: Medium sensitivity red sensitive emulsion layer Emulsion C Silver amount 0.12g
Emulsion D Silver amount 0.12g
Silver bromide emulsion covered inside (average sphere equivalent diameter 0.11μm cubic grains)
0.01g silver
Gelatin 0.60g
Coupler C-1 0.16g
Coupler C-2 7.0mg
Compound Cpd-D 1.5mg
High boiling point organic solvent Oil-5 0.050g
High boiling point organic solvent Oil-10 0.010g
Compound Cpd-T 2.0 mg.

Eighth layer: High sensitivity red sensitive emulsion layer Emulsion E Silver amount 0.32g
Emulsion F Silver amount 0.14g
Fine-grain silver iodobromide (silver iodide content 0.1 mol%, average sphere equivalent diameter 0.05 μm)
Gelatin 1.50g
Coupler C-1 0.75g
Coupler C-2 0.025g
Coupler C-3 0.020g
UV absorber U-1 0.010g
High boiling point organic solvent Oil-5 0.25g
High boiling point organic solvent Oil-9 0.05g
High boiling point organic solvent Oil-10 0.10g
Compound Cpd-D 5.0mg
Compound Cpd-L 1.0mg
Compound Cpd-T 0.020g
Additive P-1 0.010g
Additive P-3 0.030 g.

Ninth layer: Intermediate layer Gelatin 0.50g
0.10g of additive P-2
Dye D-5 0.020g
Dye D-9 6.0mg
Compound Cpd-I 0.020g
Compound Cpd-O 3.0mg
Compound Cpd-P 5.0mg
High boiling point organic solvent Oil-6 0.050 g.

10th layer: Intermediate layer Yellow colloidal silver Silver amount 3.0mg
Gelatin 1.00g
Additive P-2 0.05g
Compound Cpd-A 0.050g
Compound Cpd-D 0.030g
Compound Cpd-M 0.10 g
High boiling point organic solvent Oil-3 0.010g
High boiling point organic solvent Oil-6 0.10 g.

11th layer: Low sensitivity green sensitive emulsion layer Emulsion G Silver amount 0.07g
Emulsion H Silver amount 0.31g
Emulsion I Silver amount 0.31g
Gelatin 1.00g
Coupler C-4 0.013g
Coupler C-5 0.080g
Coupler C-10 0.020g
Compound Cpd-B 0.012g
Compound Cpd-G 3.0mg
Compound Cpd-K 2.4mg
High-boiling organic solvent Oil-2 0.024g
High boiling point organic solvent Oil-5 0.024g
Additive P-1 5.0 mg.

Layer 12: Medium sensitivity green sensitive emulsion layer Emulsion I Silver amount 0.15g
Emulsion J Silver amount 0.28g
Gelatin 0.70g
Coupler C-4 0.20g
Coupler C-5 0.10g
Coupler C-6 0.010g
Coupler C-10 0.010g
Compound Cpd-B 0.030g
Compound Cpd-U 9.0mg
High boiling point organic solvent Oil-2 0.015g
High boiling point organic solvent Oil-5 0.030g
Additive P-1 0.010 g.

13th layer: High sensitivity green sensitive emulsion layer Emulsion K Silver amount 0.30g
Silver bromide emulsion coated inside (average sphere equivalent diameter 0.11 μm cube)
Silver amount 3.0mg
Gelatin 1.20g
Coupler C-4 0.33g
Coupler C-5 0.20g
Coupler C-7 0.10g
Compound Cpd-B 0.030g
Compound Cpd-U 0.030g
Additive P-1 0.10 g.

14th layer: Yellow filter layer Yellow colloidal silver Silver amount 2.0mg
Gelatin 1.0g
Compound Cpd-C 0.010g
Compound Cpd-M 0.020g
High-boiling organic solvent Oil-1 0.020g
High boiling point organic solvent Oil-6 0.020g
0.25 g of a microcrystalline solid dispersion of dye E-2.

15th layer: Low sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.07g
Emulsion M Silver amount 0.05g
Emulsion N Silver amount 0.09g
Gelatin 0.80g
Coupler C-8 0.050g
Coupler C-10 0.50g
Compound Cpd-B 0.020g
Compound Cpd-I 10.0mg
Compound Cpd-K 1.5mg
UV absorber U-5 0.015g
Additive P-1 0.020 g.

16th layer: Medium sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.08g
Emulsion O Silver amount 0.08g
Gelatin 0.65g
Coupler C-8 0.050g
Coupler C-10 0.30g
Compound Cpd-B 0.010g
Compound Cpd-E 0.020g
Compound Cpd-N 2.0 mg
UV absorber U-5 0.015g
Additive P-1 0.020g
17th layer: High sensitivity blue-sensitive emulsion layer Emulsion P Silver amount 0.20g
Emulsion Q Silver amount 0.19g
2.00g gelatin
Coupler C-8 0.10g
Coupler C-10 1.10g
Coupler C-3 0.010g
High boiling point organic solvent Oil-5 0.020g
Compound Cpd-B 0.060g
Compound Cpd-D 3.0mg
Compound Cpd-E 0.020g
Compound Cpd-F 0.020g
Compound Cpd-N 5.0mg
UV absorber U-5 0.060g
Additive P-1 0.010 g.

18th layer: 1st protective layer gelatin 0.70g
UV absorber U-1 0.020g
UV absorber U-5 0.030g
UV absorber U-2 0.10g
Compound Cpd-B 0.030g
Compound Cpd-O 5.0mg
Compound Cpd-A 0.030g
Compound Cpd-H 0.20g
Dye D-1 8.0mg
Dye D-2 0.010g
Dye D-3 0.010g
High boiling point organic solvent Oil-3 0.040 g.

19th layer: 2nd protective layer Colloidal silver Silver amount 2.5mg
Fine-grain silver iodobromide emulsion (average sphere equivalent diameter 0.06 μm, silver iodide content 1 mol%)
Silver amount 0.10g
Gelatin 0.80g
UV absorber U-2 0.030g
UV absorber U-5 0.030g
High boiling point organic solvent Oil-3 0.010 g.

20th layer: 3rd protective layer gelatin 1.00g
Polymethylmethacrylate (average particle size 1.5 μm)
0.10g
6: 4 copolymer of methyl methacrylate and methacrylic acid (average particle size 1.5 μm) 0.15 g
Silicone oil SO-1 0.20g
Surfactant W-1 0.020g
Surfactant W-2 0.040g
In addition to the above composition, additives F-1 to F-9 were added to all the emulsion layers. Further, gelatin hardener H-1 and coating and emulsifying surfactants W-2, W-3, and W-4 were added to each layer in addition to the above composition.

  Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

The coating film thickness in the dry state of the sample 101 prepared as described above was 25.3 μm, and the swelling ratio when swollen with distilled water at a temperature of 25 ° C. was 1.88 times.

Preparation of organic solid disperse dye (Preparation of microcrystalline solid dispersion of dye E-1)
100 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF and water were added to the wet cake of dye E-1 (270 g as the net amount of E-1) and stirred to 4000 g. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultraviscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec through the slurry at a discharge rate of 0.51 / min for 2 hours. Crushed. The beads were filtered off, diluted with water to 3% dye concentration, and then heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained fine dye particles was 0.30 μm, and the breadth of the particle size distribution (standard particle size deviation × 100 / average particle size) was 20%.

(Preparation of microcrystalline solid dispersion of dye E-2)
270 g of water and W-3 were added to 1400 g of E-2 wet cake containing 30% by mass of water and stirred to obtain a slurry having an E-2 concentration of 40% by mass. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm are filled into a crusher, Imex Co., Ltd. Ultra Viscomill (UVM-2), and the peripheral speed is about 10 m / sec and the discharge rate is 0.5 L / min through the slurry. Milled for 8 hours. This was diluted with ion-exchanged water to 20% by mass to obtain a microcrystalline solid dispersion of E-2. The average particle size was 0.15 μm.

  A part of the sample 101 is cut into strips, and sensitometry is performed by the method described in the text through the above-mentioned development processing A, and the red-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, the blue As a result of obtaining the centroid wavelength of the spectral sensitivity distribution of the light sensitive silver halide emulsion layer, they were 619 nm, 548 nm and 443 nm, respectively. In addition, the third layer: the short-wave green-sensitive interimage effect imparting layer and the fourth layer: the red-sensitive interimage effect imparted layer were each applied as a single layer, and the result of obtaining the center wavelength of the spectral sensitivity distribution from the silver development density. The short-wave green-sensitive interimage effect imparting layer was 522 nm, and the red-sensitive interimage effect imparting layer was 652 nm. The silver developing process is a developing process in which, after the first washing of the developing process A, the intermediate process is skipped and the process steps after fixing are performed.

  (2) Sample 102 (comparative example): Preparation of a sample excluding the red-sensitive interimage effect imparting layer.

  The fourth layer: the red-sensitive interimage effect imparting layer was deleted from the sample 101, and the change in gradation and color balance caused by this was corrected by the ratio of the emulsions in each silver halide emulsion layer to prepare a sample 102.

  (3) Sample 103 (comparative example): Preparation of a sample excluding the short-wave green-sensitive interimage effect imparting layer.

  The third layer: the short-wave green-sensitive inter-image effect imparting layer was deleted from the sample 101, and the change in gradation and color balance caused thereby was corrected by the same means as 102 to prepare the sample 103.

  (4) Sample 104 (comparative example): Preparation of a sample excluding both the red sensitivity and the short wave green sensitivity interimage effect imparting layer.

  From Sample 101, the third layer: the short-wave green-sensitive inter-image effect imparting layer, the fourth layer: the red-sensitive inter-image effect imparting layer, and the fifth layer: the intermediate layer are deleted, and the resulting change in gradation and color balance is removed. A sample 104 was prepared by correcting the sample in the same manner as in 102.

  (5) Sample 105 (present invention): Preparation of a sample in which the spectral sensitivities of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer were changed.

  Silver halide emulsions A ′ to F ′ were prepared by changing the ratios of the spectral sensitizing dyes S-2 and S-8 used for the red-sensitive silver halide emulsions A to F used in the sample 101. Replaced with F.

  Further, the amount of the emulsion of the third layer: the shortwave green-sensitive interimage effect imparting layer was changed as follows, and the resulting gradation and color balance change were corrected by the emulsion ratio of each silver halide emulsion layer to obtain Sample 105. .

Third layer (after change): Short-wave green-sensitive interimage effect imparting layer Emulsion R Silver amount 0.01 g
Emulsion S Silver amount 0.015g
Emulsion T Silver amount 0.08g
Fine grain silver iodide (average sphere equivalent diameter 0.05μm)
0.005g silver
Gelatin 0.5g
Compound Cpd-M 0.030g
High boiling point organic solvent Oil-6 0.030g
High boiling point organic solvent Oil-7 5.0mg
Dye D-7 4.0 mg.

(6) Sample 106 (Comparative Example): Preparation of Sample Excluding Red Sensitive Interimage Effect-Providing Layer Fourth Layer from Sample 105: Red Sensitive Interimage Effect-Providing Layer is Deleted, and the resulting gradation and color balance Sample 106 was prepared with the change corrected by the emulsion ratio of each silver halide emulsion layer.

(7) Sample 107 (Comparative Example): Preparation of Sample Excluding Short Wave Green Sensitive Inter Image Effect-Providing Layer Third Layer: Short Wave Green Sensitive Inter Image Effect-Providing Layer is Deleted from Sample 105, and Tone and Color Generated thereby A change in balance was corrected by the same means as 106 to prepare a sample 107.

(8) Sample 108 (Comparative Example): Preparation of Sample Excluding Both Red Sensitivity and Short Wave Green Sensitivity Inter Image Effect Giving Layer From Sample 105, Third Layer: Short Wave Green Sensitivity Inter Image Effect Giving Layer, Fourth Layer: Red sensitive interimage effect imparting layer, fifth layer: The intermediate layer was deleted, and the change in gradation and color balance caused thereby was corrected by the same means as 106 to prepare a sample 108.

(9) Sample 109 (Invention): Preparation of Sample Introducing Short-Wave Blue-Sensitive Interimage Effect-Providing Layer Sample 14: 14th layer: Yellow filter layer and 15th layer: Low-sensitivity blue-sensitive emulsion layer Sample 109 was prepared by inserting the short-wave blue-sensitive interimage effect imparting layer and correcting the change in gradation and color balance caused by the same means as Sample 102.

  The center-of-gravity wavelength of the spectral sensitivity of the short-wave blue-sensitive interimage effect imparting layer was 430 nm.

Short-wave blue-sensitive interimage effect imparting layer Emulsion V Silver content 0.20 g
Gelatin 0.40g
Coupler C-1 5.0mg
Coupler C-2 0.5mg
High boiling point organic solvent Oil-5 2.0mg
Compound Cpd-Q 0.20g
Dye D-6 4.0mg
The characteristics of the samples 101 to 109 are collectively shown in Table 10 below.

(Sample evaluation)
The above-mentioned samples 101 to 109 were cut into strips, and sensitometry was performed by the following method.
By multiplying the spectral reflectance of “skin color” in Table 1 and “Gray” shown in Table 2 by the spectral distribution of ISO daylight (D55), the spectral distribution (relative spectral) under the standard illumination of each color is obtained. (Luminance) was calculated. The above spectral distribution is generated using a spectral sensitometer that creates an arbitrary spectral distribution by electrically controlling the transmittance of each liquid crystal segment using an intensity-modulated mask created by arranging liquid crystal panels in stripes. I let you. The spectral sensitometer device for generating the spectral distribution was prepared based on a report by Enomoto et al. In the 1990 Annual Meeting of SPSTJ '90. As shown in FIG. 1, a high-brightness xenon arc lamp was used as the light source, and slit light long in the grating direction of the diffraction grating was obtained by an optical system using a cylindrical lens. The light split by the transmission diffraction grating becomes a spectral plane having a wavelength range of 400 nm to 700 nm on the dispersion plane. A liquid crystal panel consisting of 60 segments with 5 nm as one segment was placed on this spectrum surface, and the transmittance was controlled every 5 nm to obtain the desired spectral distribution. On the exposure surface, mixed color slit light is made, and the samples 101 to 109 of the present invention and the commercially available color reversal films (products A to D) on which optical wedges are superimposed are scanned in a direction perpendicular to the slit light. And exposed.

In this way, the sample exposed with the spectral distribution of “gray” and “skin color” was subjected to the above-described processing (processing A), and the density of the obtained image was measured. The measurement of “skin color” reproduced with these samples was performed under observation conditions based on a color matching experiment employing a double field of view at a 1931 meeting of the CIE (International Commission on Illumination). The CIE Lab value was calculated using a CIE 1976 (L ^* , a ^* , b ^* ) uniform perceptual color space calculation method. For more detailed explanation of these, we referred to Chapter 4 of the “New Color Science Handbook”, University of Tokyo Press (1980). When the C ^* value of the “gray” image at L ^* = 40 is 0.5 or more, color correction was performed by exposing with “gray” “skin color” light through a commercially available color correction filter.

Calculated L ^*, a ^*, b ^* values from the ^L * = a chroma ^C _{* 70} at ^70, L * = chroma ^C _* 50 at ^50, L * = 20 Ratio seeking chroma ^{C *} ₂₀ in ( C ^* ₇₀ / C ^* ₅₀ ) and (C ^* ₂₀ / C ^* ₅₀ ) were obtained.

Further, in the range of L ^* = 20 to 70, the hue angle H = tan ⁻¹ (a ^* / b ^* ) was determined in increments of L ^* , and the standard deviation σh was determined.
Furthermore, the maximum value of the C * value in the range of L ^* = 20 to 70 in the CIE Lab color system of the “gray” image was obtained.

  As an example, for the sample 101 of the present invention and the sample 108 of the comparative example, a CIE Lab value is obtained for an image obtained by performing wedge exposure and processing with a spectral distribution of “skin color”, and the lightness L * is in the range of 20 to 70. The change in saturation C * and the change in hue angle H are shown in FIGS. 2 and 3 below. It can be seen that the sample of the present invention has a smaller change in saturation C * and hue angle H with respect to lightness L * than in the comparative example.

(Skin color shooting under normal conditions)
Furthermore, the above sample is cut into a brownie size of 60 mm, processed, loaded into a camera, and photographed with white and male and Japanese (yellow race) men and women with large strobe light (color temperature 4950K) through a diffuser indoors. Then, the above-described development processing was performed and visually evaluated. At the same time taking the color chart of the Macbeth color chart number 22 (Gray 5), C ^* value is C ^* value with a commercially available color correction filter in the same manner as in the evaluation of the spectral sensitometer in the case of more than 0.5 Was corrected to be 0.5 or less. The evaluation was performed by 10 people. Regarding “Reproduction of skin tone”, “Saturation of skin color”, and “Floating redness of skin color”, “Unfavorable” was 0, “Normal” was 1, and “Very favorable” was 2 Scores were assigned as points, and the average score was used as the evaluation value.

(Skin color shooting in the shade)
Similar to the above skin color photography, the same color correction filter conditions as skin color photography were used, and the same female model as skin color photography and Macbeth color chart number 22 color chart were put in the shade of the building outdoors in fine weather. . The color temperature at the time of photographing was 8500K. Next, the above-described development processing was performed and visually evaluated.

  The evaluation was performed by 10 people, and for “the degree of blue fog”, “sad” was scored as 0, “ordinary” was scored as 1, “very favorable” was scored as 2, and the average score was calculated. It was set as an evaluation value for shadow photography.

(Shooting under fluorescent light)
Similar to the above skin color photography, the same color correction filter conditions as skin color photography are used indoors under a white fluorescent lamp (National FLR40S / W / MX) and a three-wavelength fluorescent lamp (National FLR40S / EX-D / In M), the same female model and Macbeth color chart number 22 (gray 5) color chart were put in and photographed. Next, the same development processing was performed and visually evaluated.

  The evaluation is also performed by 10 people, and for “the degree of green fog”, the score is given as “unfavorable” 0 points, “ordinary” 1 point, “very favorable” 2 points, the average score It was set as the evaluation value of fluorescent lamp photography.

(Color chart shooting)
A total of 40 color charts having spectral reflectances shown in Table 9 and gray charts of Macbeth color chart numbers 19 to 24 were simultaneously photographed under normal photographing conditions, and the same development processing A was performed. The CIE Lab value was determined by measuring the spectral absorption spectrum of all the 40 colors with the above-described method for the frame where the density of Macbeth color chart number 22 was 0.8 ± 0.03 in the obtained image. From the values of a * and b * obtained, the hue angle Hi (where i is the color chart number 1 to 40) and the Lab value of the original color chart are obtained in the same manner to obtain the original hue angle Hoi (i = 1 to 40), ΔH representing the fidelity of color reproducibility was obtained. However, ΔH is expressed by the following formula.

The closer the value of ΔH is to 0, the more faithfully the original hue is reproduced.

These data are summarized in Table 10. As a result, the sample 101 of the present invention has a skin color with a small saturation difference from high brightness to low brightness and a small hue change, as compared with the comparative examples 102, 103, and 104 that do not have both inter-image effect imparting layers. From the result of actually shooting a person, the saturation of the skin color is high, the tone reproduction is excellent, and the `` redness in the skin color '' that tends to occur when the saturation of the skin color is high is suppressed to a small level. Excellent skin color reproducibility.

  Furthermore, this sample has a feature that “blue fog when shooting in the shade” and “green fog when shooting under fluorescent light” are also small. The value of ΔH obtained by actually evaluating the fidelity of color reproducibility for various colors within the color coordinates is also smaller than that of the comparative example, and has faithful color reproduction performance. The gray reproducibility is excellent by maintaining a good gray from low to high brightness.

  It can be seen that the sample 105 having a long wave center wavelength of the red-sensitive silver halide emulsion layer is inferior to the sample 101 in terms of fidelity of color reproducibility, but is excellent in skin color reproducibility as in the sample 101.

  In addition to the short-wave green-sensitive inter-image effect imparting layer and red-sensitive inter-image effect imparting layer of the present invention, the sample 109 having the short-wave blue-sensitive inter-image effect imparting layer is also excellent in skin color reproduction, similar to the sample 101 of the present invention. It can be seen that it has a desirable performance that combines color reproducibility with high fidelity.

The schematic diagram of a spectrophotometer apparatus. The graph which shows the change of the chroma C * with respect to L * in the range whose brightness L * of the sample 101 of this invention and the comparative example 108 is 20-70. The graph which shows the change of the hue angle H with respect to L * in the range whose brightness L * of the sample 101 of this invention and the comparative example 108 is 20-70.

Claims (1)

At least one blue-sensitive silver halide emulsion layer containing a yellow color coupler, at least one green-sensitive silver halide emulsion layer containing a magenta color coupler, and a red-sensitive silver halide emulsion layer containing a cyan color coupler on a transparent support. In the silver halide color reversal photographic light-sensitive material having, in addition to the blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, the photographic light-sensitive material has the following interimage effect-imparting layers (a) and (b): In a “skin color” image reproduced with the photographic light-sensitive material when the photographic light-sensitive material has at least one layer and is exposed to “skin color” light having the spectral reflectance distribution shown in Table 1 below and developed, CIE Lab a chroma ^C _{* 70} in lightness ^L * = 70 represented by the color system, the lightness ^L * = ratio of chroma ^C _{* 50} at _{^{50 (C * 70 / C *}} 50) is And wherein the at .7 above, silver halide color reversal photographic material.
(A) An inter-image effect imparting layer containing a short-wave green-sensitive silver halide emulsion having a spectral sensitivity distribution having a centroid wavelength of 500 nm or more and 560 nm or less.
(B) An inter-image effect imparting layer containing a red-sensitive silver halide emulsion having a spectral sensitivity distribution with a centroid wavelength of 580 nm to 700 nm.

Images