JP2873890B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which is desirably decolorized and / or decolored so as not to cause residual color contamination by being developed.
Or a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted.

[0002]

2. Description of the Related Art In general, silver halide photographic materials are used for the purpose of adjusting sensitivity, improving safelight safety, adjusting light color temperature, preventing halation, or adjusting the sensitivity balance of a multilayer color photographic material. It has been conventional to include a light absorbing compound in a silver halide emulsion layer or other hydrophilic colloid layer in order to absorb light of a specific wavelength. For example, a silver halide photographic light-sensitive material is formed by forming a hydrophilic colloid layer such as a photosensitive silver halide emulsion layer on a support, and an image is formed on the photosensitive silver halide emulsion layer to record an image. When performing uniform exposure, it is necessary to control the spectral composition of light incident on the silver halide emulsion layer in order to improve photographic sensitivity. In such a case, a dye capable of absorbing light in a wavelength range unnecessary for the silver halide emulsion layer is usually added to a hydrophilic colloid layer present on a side farther from the support than the photosensitive silver halide emulsion layer. A method is used in which a filter layer is contained to transmit only light in a target wavelength range. For the antihalation layer, an antihalation layer is provided between the photosensitive emulsion layer and the support or on the back surface of the support for the purpose of improving the sharpness of the image, and the interface between the emulsion layer and the support is provided. And harmful reflected light at the back of the support is absorbed to improve the sharpness of the image. Further, in the silver halide emulsion layer, a dye capable of absorbing light in a wavelength range sensitive to silver halide may be used for the purpose of preventing irradiation in order to increase the sharpness of an image. In particular, silver halide photographic light-sensitive materials used in the photoengraving process, more specifically light-room light-sensitive materials, use a dye or a light source that absorbs UV light or visible light to enhance safety against safelight light. And a photosensitive layer. Further X
In a line-sensitive material, a colored layer for improving sharpness may be provided as a crossover cut filter for reducing crossover light. In a microfilm, the antihalation layer provided between the photosensitive emulsion layer and the support may also serve as a light-shielding layer for improving the light room loading suitability.

The layers to be colored often consist of hydrophilic colloids, so that for their coloring usually a dye is included in the layers. This dye must satisfy the following conditions. (1) To have appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer must not be adversely affected in a chemical sense, for example, decrease in sensitivity, regression of a latent image, or fogging. (3) Decoloring during photographic processing but not dissolving and removing, leaving no harmful coloring on the processed photographic light-sensitive material. (4) It has excellent stability over time in a coating solution (solution) or a silver halide photographic material and does not deteriorate. And other conditions must be satisfied.

Many efforts have been made to find dyes that meet these conditions. When the layer containing the dye functions as a filter layer, an antihalation layer,
It is necessary that the layer be selectively colored and that the other layers be substantially uncolored. This is because, when the other layers are also substantially colored, not only do they have detrimental spectral effects on the other layers, but also the effects of the filter layer and the antihalation layer are reduced.

As a method for solving this problem, a method in which a so-called acid dye having a sulfo group or a carboxyl group is localized in a specific layer by using a mordant,
Nos. 6-12639, 55-155350, 55-
155351, 52-92716, 63-19
No. 7943, No. 63-27838, No. 64-4082
7, European Patent Nos. 0015601B1 and 027
It is known to disperse dyes as dispersed solids, as disclosed in US Patent No. 6566A1, WO 88/04794.

[0006]

However, most dyes used as a dispersion of this kind of dye control the fixing and the decolorization by the dependence of the dissociation of the carboxyl group on the hydrogen ion concentration (pH). Things. Although it is substantially water-insoluble at a pH of 6 or less, it is not sufficiently fixed in a silver halide photographic light-sensitive material and diffuses to other layers, or dissociation and dissolution proceeds during storage to change the hue. Diffusion into other layers has been a problem. It has been known that when diffused into another layer, a filter may be desensitized, or may be adversely affected by photography due to adsorption to silver halide grains. In particular, adverse effects have been observed with the pyrazolone oxonol dyes represented by the aforementioned general formulas disclosed in JP-A-52-92716 and JP-A-64-40827.

It is an object of the present invention to provide a hydrophilic colloid layer in which only a desired hydrophilic colloid layer is sufficiently selectively dyed by a dye, and which has excellent decoloration by photographic processing (especially low pH rapid processing). To provide a silver halide photographic light-sensitive material. A second object of the present invention is to provide a silver halide photographic material in which the hydrophilic colloid layer is colored by a dye which is irreversibly decolorized by photographic processing and which has excellent storage stability.

[0008]

The inventors of the present invention have studied to solve the above problems, and as a result, at least one photosensitive silver halide emulsion layer and at least one layer represented by the following general formula on a support. In a silver halide photographic material having a hydrophilic colloid layer containing a dispersed solid of the dye (I),
The absorption spectrum based on the dye (I) in the hydrophilic colloid layer containing the dispersed solid of the dye (I) was 680 nm.
Is the ratio of the absorbance at 530 nm to the absorbance at
The first diffraction intensity and the diffraction angle 2θ of the silver halide photographic light-sensitive material and / or the dye (I) at X-ray diffraction angle 2θ of 26 to 27 degrees are 14 The ratio of the second-order diffraction intensity in degrees is 1.3
It has been found that this is achieved by a silver halide photographic light-sensitive material characterized by being 0 or less.

[0009]

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(However, R and R 'in the above general formula
Represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an ester group, respectively. Among the dyes (I), a compound represented by the following dye (II) is particularly preferably used. )

[0011]

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The dye (I) used in the present invention is disclosed in various patents such as JP-A-52-92716, Japanese Patent Application No. 1-87367, Japanese Patent Application No. 2-34738, and Japanese Patent Application No. 2-247927. As described in JP-A-52-92716, the absorption spectrum based on the dye (II) is obtained by dispersing the dye (II) synthesized according to a known synthesis method in a solid state. This has a high absorption around 680 nm, which is easily dissociated by temperature and humidity and diffuses into other layers in the photographic material. The absorption in practical photographic light-sensitive materials also has a relatively high absorption at around 680 nm, and there is no description in the above patents or other patents regarding the spectrum having a low absorption at around 680 nm. It can be considered that a spectral pattern described in US Pat. The absorption based on the non-dissociated aggregate of dye (II) is a very broad absorption around 530 nm, and the absorption intensity around 680 nm is relatively low.
The lower the absorption intensity around 30 nm, the smaller the change due to temperature and humidity. In the present invention, the ratio of the absorbance at 680 nm to the absorbance at 530 nm is preferably 0.50 or less, more preferably 0.40 or less.

[0013] If we measure the X-ray diffraction of the dye (II), or repeatedly arranged only in a one-dimensional direction, it is suggested, which is a kind of layered compound, corresponding to the plane interval 3.3 Å There is a first diffraction peak at a diffraction angle 2θ of 26 to 27 degrees, and a higher diffraction peak is observed based on the first diffraction peak. The diffraction pattern of the dye (II) synthesized by the above-mentioned known synthesis method shows that the intensity of the first-order diffraction peak at a diffraction angle 2θ of 26 to 27 degrees indicates that the diffraction angle 2θ is 1
It can be seen that the intensity of the second diffraction peak at 4 degrees is very strong, and that the dye (II) according to the present invention has the second diffraction peak.
It is found that the intensity of the next diffraction peak is relatively strong, and that the peak is sharpened, which is interpreted as that the regularity of the molecular arrangement is increased. In the present invention, the ratio of the first-order diffraction intensity at a diffraction angle 2θ of 26 to 27 degrees and the second-order diffraction intensity at a diffraction angle 2θ of 14 degrees is 1.30 or less, and preferably 1.20. It is as follows.

There is some correlation between the ratio of the above-mentioned diffraction intensity and the ratio of the absorbance in the above-mentioned absorption spectrum. The smaller the ratio of the diffraction intensity, the smaller the ratio of the absorbance.
Although the change in the absorption spectrum due to humidity and heat tends to be small, the absorption spectrum may be different even if the X-ray diffraction pattern is the same, depending on the dispersant, disperser, dispersion conditions, etc. when dispersing into a solid state. I can't say it.

The dye according to the present invention is subjected to a molecular alignment promoting treatment before being incorporated into a light-sensitive material, whereby the preferred absorption spectrum and / or X-ray diffraction pattern of the present invention can be obtained. Heat treatment, ultrasonic treatment, mechanical treatment, high-frequency treatment, etc. are effective as the molecular alignment promoting treatment.
In particular, it is preferably performed in a wet state or in a solvent, and heat treatment or high-frequency treatment is particularly preferable. The heat treatment is performed in a drying step after the synthesis of the dye, or a method performed before the step of finely dispersing the dye powder into a solid state by heating the dye powder in a solvent, and a method in which the dye is dissolved in water or in the presence of a dispersant. When dispersing in another solvent, there are a method of performing dispersion without cooling or applying a temperature, and a method of heat-treating the liquid or coating liquid after dispersion.

The temperature of the heat treatment varies depending on the heat treatment process, the size and shape of the powder or particles, the heat treatment conditions, the solvent, and the like. However, when heat-treating with a powder, the temperature is 40 ° C to 200 ° C, preferably 50 ° C.
To 150 ° C, 40 ° C to 150 ° C, preferably 50 ° C to 150 ° C when heat-treating in a solvent, 40 ° C to 90 ° C, preferably 50 ° C to 90 ° C, when heat-treating during dispersion. When the dispersion liquid is subjected to a heat treatment, the temperature is 40 ° C to 100 ° C, preferably 50 ° C to 95 ° C.

For effective heat treatment, the heat treatment is preferably carried out in a solvent. The type of the solvent is not particularly limited as long as it does not substantially dissolve the dye (I).
Water, alcohols (eg, methanol, ethanol,
Isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol, diethylene glycol, ethyl cellosolve), ketones (eg, acetone, methyl ethyl ketone), esters (eg, ethyl acetate, butyl acetate), alkyl carboxylic acids (eg, acetic acid, propion) Acid), nitriles (eg, acetonitrile), ethers (eg, dimethoxyethane, dioxane, tetrahydrofuran) and the like.

When an organic carboxylic acid coexists during the heat treatment, the object of the present invention can be more effectively solved.
Examples of the organic carboxylic acids include alkyl carboxylic acids (for example, acetic acid and propionic acid), carboxymethyl celluloses (CMC), and aryl carboxylic acids (for example, benzoic acid and tilicilic acid). When the amount of the organic carboxylic acid is used as a solvent, the amount of the dye (I)
0.5 to 100 times the weight of When an organic carboxylic acid is added using a solvent other than the organic carboxylic acids, the amount of the organic carboxylic acid is 0.05 to 100% with respect to the dye (I).
It can be used at a weight ratio of 100%.

The time for the heat treatment is also unconditional, and a lower temperature requires a longer time and a higher temperature requires a shorter time. The heat treatment can be arbitrarily set within a range that does not affect the manufacturing process, but it is usually 1 hour to 4 days.

As a method for dispersing the dye into solid particles, as described in JP-A-52-92716, WO88 / 04794, a dispersing machine such as a ball mill, a sand mill and a colloid mill, a roll mill, and various types of vertical or horizontal media. A disperser, a disperser such as Mantongaurin, a microfluidizer, and a disk impeller mill can be arbitrarily selected, but a medium disperser is preferable.

When dispersing the dye into solid particles, an anionic surfactant may be used as described in JP-A-52-92716, WO88 / 04794, etc. As described above, an anionic polymer can be used, and if necessary, a nonionic or cationic surfactant can be used. However, an anionic polymer or an anionic surfactant is preferable.

The dye of the present invention is incorporated into a hydrophilic colloid layer in the form of a solid particulate dispersion and used for various purposes. The addition position is not specified since it varies depending on the purpose of use, but it may be used as an antihalation layer, a crossover cut layer, or a light-shielding layer from the back side by coating between the support and the silver halide emulsion layer. It can be added to a silver halide emulsion layer to prevent irradiation. Further, it can be used as a filter layer, particularly a safelight filter layer, by coating the silver halide emulsion layer on the upper side (outside of the support).

The amount of the dye to be applied to the hydrophilic colloid layer in the state of the solid particle dispersion used in the present invention depends on the type of the dye, the required absorbance, and the like, and cannot be specified unconditionally. ^{1mg / m 2 ~300mg / m 2} , preferably ^{3mg / m 2 ~200mg / m 2} .

Gelatin is preferred as a preferred hydrophilic colloid. Since the dye of the present invention can be used for both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials, the coating amount of gelatin can not be specified without any limitation, but it is on the same side of the support as the layer containing the dye dispersion. 1.5% total gelatin coating
g / m ^{2 to} 30 g / m ^2, more preferably 1.5 g / m ²
２０20 g / m ² . Amount of gelatin layer containing the dye dispersion is 20mg ^{/ m 2} ~3g ^/ m 2 is preferred. In particular, from the viewpoint of speeding up the processing, it is preferable to reduce the coating amount of the hydrophilic colloid as much as possible. In one preferred embodiment, the layer containing the dye dispersion is provided between the support and the silver halide emulsion layer. And the coating amount of the hydrophilic colloid of the dye layer is 0.5 g / m ² or less, preferably 20 mg / m ² to
It can be an undercoat layer of 300 mg / m ² . The silver halide photographic light-sensitive material of the present invention can be a double-sided light-sensitive material. Various types of gelatin are known, and lime treatment, acid treatment, or various modified gelatins can be used.

The solid particulate dispersion of the dye of the present invention can be used alone as a dye in a photographic material.
It can be used in the same layer together with other solid particulate disperse dyes, or it can be used in another layer. For example, a dye dispersion of the present invention and a solid particulate dispersion of a shorter-wave yellow dye are mixed and used as an antihalation layer, or a solid particulate dispersion of a longer-wave infrared dye is mixed. Can be used as an antihalation layer. Further, the dye dispersion of the present invention can be used as an antihalation layer, and a solid particulate dispersion of a short-wave yellow dye can be used as a filter layer. For the dispersed solid dye which can be used in combination with the dye dispersion of the present invention, W
There are detailed descriptions in O88 / 04794, Japanese Patent Application No. 2-118042, and Japanese Patent Application No. 3-121749, and any of them can be used in combination. It is also possible to add the solid particulate dispersion of the dye of the present invention to two or more layers. Since the dye dispersion of the present invention is fixed to a specific layer,
For example, a necessary amount can be incorporated as an antihalation layer, and a necessary amount can be added to a silver halide emulsion layer for preventing irradiation.

As the dye, a known water-soluble dye can be used in combination, if necessary. Further, a dispersion in which an oil-soluble dye is emulsified or dispersed in a polymer can be used in combination, if necessary.

Although the particle size of the solid particulate dispersion of the dye of the present invention varies depending on the purpose, it is preferable that the particle size is fine due to restrictions such as addition to a thin gelatin layer and decolorization by short-time treatment. 0.05 in particle size
μm to 2 μm, more preferably 0.05 μm to 1 μm, even more preferably 0.05 μm to 0.6 μm
m.

The solid-dispersed dye of the present invention is decomposed and eluted by hydroquinone, sulfite, alkali or the like in a developing solution during development processing, so that the photographic image is not colored or stained. The time required for decolorization is the hydroquinone concentration in the developing solution or other processing baths, the amount of sulfite, alkali or other nucleophile, the type and amount of the compound, the position of addition, the amount and swelling degree of the hydrophilic colloid, Since it greatly depends on the degree of stirring and the like, it cannot be unconditionally specified. It can be arbitrarily controlled according to general rules of physical chemistry. Processing liquid p
H varies depending on development, bleaching, fixing and the like, but is usually pH 3.0
-13.0, more preferably pH5.
It is in the range of 0 to 12.5. Accordingly, the compounds of the present invention are characterized in that dye units can be released by such a relatively low pH processing solution. In the photographic light-sensitive material containing a light-sensitive silver halide emulsion layer used in the present invention, usually, light-sensitive materials used in this field are used, and silver halide emulsions and the like which are also used in this field are applied. You. For example, JP-A-3-13936 and 3-1393
The light-sensitive materials, silver halide emulsions and the like described in JP-A No. 7 can be applied. More specifically, JP-A-3-139
No. 88, page 36, lower right column, line 8, “Silver halide grains used in the present invention” to “cut” in page 9, upper left column, line 9, line 9. Silver halide photographic emulsion, a light-sensitive material containing the same, a support thereof, a processing method thereof, an exposure method and the like are similarly employed in the present invention.

[0029]

【Example】

Example 1 1- (4-carboxyphenyl) -3-methyl-2-pyrazolin-5-one (26.2 g), glutaconaldehyde dianyl hydrochloride (14.2 g), N, N-dimethylformamide (200 ml) ) Was added to the mixture, and the mixture was stirred at room temperature for 1 hour. After methanol (100 ml) was added to the reaction solution and the mixture was filtered off with dust, a hydrochloric acid-methanol solution (53 ml of 36% concentrated hydrochloric acid and methanol 8) was added.
0 ml of a mixture) was added dropwise at 20-25 ° C. with stirring for 15 minutes. After stirring for 30 minutes at 20 to 25 ° C after dropping,
The product was filtered off with suction and washed with methanol (3 × 200 ml). Then wash with water until the filtrate is neutral,
83 g of a water wet product of dye (II) (dye content: 28.5%)
I got 60 g of the water wet product was blow-dried (1 week) at room temperature. A weight of 17.1 g after drying was obtained. This is the dye
II-.

60 g of a water wet product of the dye (II) is
The mixture was dried by heating at a normal pressure at a temperature of 3 ° C. for 3 days. Weight 17.1 after drying
g was obtained, which was designated as Dye II-. Dye II-10g
The mixture was heated and refluxed for 8 hours while stirring, cooled to room temperature, and the solid content was removed by suction filtration. 25 g of a water-moistened dye (II) having been heat-treated (the content of the dye was 40%) was obtained. This was designated as Dye II-.

To 10 g of Dye II-10 ml of acetic acid was added,
The mixture was heated and refluxed at 105 to 110 ° C for 7 hours. After cooling to room temperature, the solid content was removed by suction filtration. The obtained solid was washed once with 100 ml of methanol and four times with 50 ml of water to obtain 18 g of a heat-treated wet product of dye (II) in water (dye content: 55.6%). This was designated as Dye II-. To 10 g of Dye II-1 was added 100 ml of a 1% aqueous solution of carboxymethyl cellulose, and the mixture was heated and refluxed for 8 hours.
After cooling to room temperature, an aqueous suspension was obtained. This was designated as Dye II-.

Example 2 The dye powder synthesized in Example 1 (wet matter suspension was dried at room temperature) was gently rubbed with an agate mortar, and rubbed into a holder for X-ray diffraction measurement. It was measured with a meter. Measurement is diffraction angle 2θ
From 5 ° to 60 °. Representative measurement charts are shown in FIGS. 1 and 2. Although there are slight deviations, three distinct peaks were observed for this oxonol dye. These were 7 °, 14 °, 26-27 °. Table 1 shows the ratio between the first-order diffraction intensity when the diffraction angle 2θ is 26 to 27 degrees and the second-order diffraction intensity when the diffraction angle 2θ is 14 degrees. The dye according to the synthesis method of the present invention had a small diffraction intensity ratio of 1.30 or less, which was different from the comparative example synthesized by the conventional synthesis method, and a completely unexpected change was observed.

[0033]

[Table 1]

Example 3 <Preparation of Dispersion A (Comparative Example)> JP-A-52-92716
According to Example 1 of No. 1, a small amount of water was added to 1.34 g of sodium oleylmethyl tauride as a dispersant in 50 g of Dye II, and then premixed.
The dispersion was adjusted to 0 g and dispersed by a sand grinder for 4 hours using Ottawa Sand as a dispersion medium. After dispersion, the resultant was diluted with water to obtain a dispersion A having a dye concentration of 2%.

<Preparation of Dispersion B (Comparative Example)> Dye II- was prepared according to the examples of International Application Publication (WO) 88/04794.
20g, Triton X-200 ^R (Rohm & Haa
water was added to 72 ml of a 5% aqueous solution (manufactured by S. Co., Ltd.) to make 500 g, and the mixture was dispersed in a vibrating ball mill for 10 hours using zirconia beads. .

<Preparation of Dispersions C to E (Invention)> According to Example 1, 3.75 g of Dye II- was added with 37.5 ml of a 1% aqueous solution of carboxymethylcellulose as a dispersant, and premixed. Then, the mixture was dispersed in zirconia beads for 3 hours using Eiger Motor Mill M-50, which is a horizontal type medium dispersion machine. The dispersion was diluted with water to give a dye concentration of 2% to obtain a dispersion C.
Dye II- was dispersed in the same manner to obtain dispersion D.
Dye II- was also dispersed in the same manner with the correction of the solid content of the dye, and was used as dispersion E.

<Preparation of Dispersion F (Invention)> The whole amount of the dye suspension II- which had been heat-treated according to Example 1 was dispersed as it was in the same manner as Dispersion C in an Eiger Motor Mill for 3 hours.
After dispersion, the resulting mixture was diluted to obtain Dispersion F. <Preparation of Dispersions G and H (Invention)> A part of the dispersions A and E was taken and heated and maintained at 85 ° C. for 6 hours. The dispersions after heating were used as dispersions G and H, respectively. <Preparation of Dispersion I (Invention)> Dispersion F was prepared in an amount of 200 ml, and subjected to high-frequency treatment for 2 minutes in a household microwave oven manufactured by Toshiba.

Example 4 <Preparation of Coated Films 4-1 to 4-9> A coated film was prepared as follows on a 180 μm polyethylene terephthalate support coated with gelatin. Gelatin 4.0 g / m ² Dispersion of dye (II) As solid content of dye 70 mg / m ² Potassium polystyrenesulfonate 25 mg / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² 1,2-bis (vinylsulfonylacetamide) Ethane 80 mg / m ² Dispersions A to I were coated and coated with coating films 4-1 to 4-1.
−9.

<Preparation of Coating Film 4-10> Dispersion F
A solution obtained by removing the hardening agent 1,2-bis (vinylsulfonylacetamide) ethane from the coating solution using
After keeping the temperature for 6 hours, the hardener that had been removed was added, and coated in the same manner as the coated film 4-1.
0 was set.

Example 5 Measurement of Spectral Absorption Spectra The coated films 4-1 to 4-10 prepared in Example 4 were stored as they were (Fresh) and at 50 ° C. and 80% RH for 3 days (Wet). ) The spectral absorption spectrum of the film was measured. The measurement was performed from 360 nm to 800 nm using a U-3210 type spectrophotometer manufactured by Hitachi, Ltd. Even if the compounds are the same, the absorbance at 530 nm and the absorbance at 680 nm differ greatly depending on the dispersion.
et storage reduces the absorbance at 680 nm,
An increase in the absorbance at 630 nm was observed, and it was confirmed that the temperature and humidity accelerated the dissociation of the dye. Table 2 shows the absorbance at 530 nm and 680 nm in Fresh.
, The absorbance ratio at 680 nm to the absorbance at 530 nm, and the change in absorbance at 630 nm due to wet storage were determined.

[0041]

[Table 2]

The coated films 4-1 and 4-2 according to the synthetic dispersion method of the comparative example were judged to have substantially similar spectra in light of the absorption spectrum shown in JP-A-52-92716. It is believed to be a known dispersion of Dye (II). In this known dispersion, the absorbance at 680 nm is relatively high, and the change in absorbance at Wet storage is large, whereas in the dispersion of the present invention, the absorbance at 680 nm is relatively low, and the change in absorbance at Wet storage is small. It is clear that there are small features.

Example 6 A silver halide emulsion was prepared as follows in order to check the performance in a photographic light-sensitive material. <Preparation of Original Emulsion # 1> Solution I 75 ° C. Demineralized inert gelatin 24 g Distilled water 90 mL KBr 4 g KI 1.7 g 10% phosphoric acid aqueous solution 2 mL Sodium benzenesulfinate 5 × 10 ^-2 mol 1,3-dimethylimidazo Lysine-2-thione 2.5 × 10 ^-3 g Solution II 35 ° C. Silver nitrate 170 g Distilled water was added to 1000 ml Solution III 35 ° C. KBr 230 g Potassium hexachloroiridate (III) (0.001% aqueous solution) 2 ml Distilled water was added. 1000 ml Solution IV room temperature Potassium hexacyanoferrate (II) 3.0 g Distilled water was added and 100 ml solution II and solution III were added to solution I and stirred at the same time for 45 minutes.
Over a period of one minute, and when the total amount of Solution II has been added, a cubic monodispersed emulsion having an average particle size of 0.28 μm is finally obtained.

At this time, the addition rate of the solution III was adjusted with respect to the addition of the solution II while adjusting the pAg value in the mixing vessel to always be 7.50. The solution IV was added over 5 minutes from 7 minutes after the start of the addition of the solution II. Solution II
After completion of the addition, the mixture was washed with water and desalted by a sedimentation method, and then dispersed in an aqueous solution containing 100 g of demineralized inert gelatin. This emulsion contains sodium thiosulfate and chloroauric acid per mole of silver.
After adding 34 mg of water salt and adjusting pH and pAg value to 7.0 and 8.9 (40 ° C.), respectively, 5 mg of sodium thiosulfate and 3 mg of N, N-dimethylthiourea were added.
And 10 mg of chloroauric acid, and then chemically sensitized at 75 ° C. for 60 minutes to obtain a surface latent image type silver halide emulsion.
At this time, as a stabilizer, 2-methyl-4-hydroxy-
50 mg of 1,3,3a, 7-tetrazaindene and 100 ppm of phenoxyethanol were added.

On a polyethylene terephthalate (PET) support having a thickness of 100 μm, a first undercoating layer made of styrene-butadiene latex was provided after the surface was subjected to a corona discharge treatment in order to improve the adhesive strength with the hydrophilic colloid layer. A second undercoat layer of gelatin 0.08 g / m ² was provided on the upper layer, and an antihalation layer, an emulsion layer, and a protective layer were sequentially coated on the second undercoat layer from the support side as described below to prepare photosensitive sheets 1 to 11. .

<Photosensitive sheet 1> Antihalation layer Gelatin 1500 mg / m ² Dispersion A As dye (II) 120 mg / m ² Potassium polystyrene sulfonate 30 mg / m ² Sodium dodecylbenzenesulfonate 8 mg / m ² Proxel 15 mg / m ² The 1,2-bis (vinylsulfonylacetamido) ethane 65 mg / m ² coating solution was applied to a 2% phosphoric acid aqueous solution after adjusting the pH to 5.6.

The emulsion layer silver halide emulsion silver content as 1500 mg / m ² gelatin as 1550mg / m ² Sensitizing dye 21 mg / m ²

[0048]

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5-methylbenzotriazole 3.6 mg / m ² sodium dodecylbenzenesulfonate 4.4 mg / m ² potassium polystyrene sulfonate 30 mg / m ² polyethyl acrylate latex (as solid content) 200 mg / m ² 1,2- The coating solution of bis (vinylsulfonylacetamide) ethane 66 mg / m ² was adjusted to pH 5.8 with a 2% aqueous phosphoric acid solution and applied.

Protective layer Gelatin 500 mg / m ² Colloidal silica 100 mg / m ² Liquid paraffin 23 mg / m ² Barium strontium sulfate (average particle size 1.5 μm) 13 mg / m ² Proxel 2 mg / m ² N-perfluorooctanesulfonyl-N - propyl glycine potassium salt _{^{2mg / m 2 C 9 H 19}} - (C 6 H 4) -O- {CH 2 CH (OH) CH 2 O} 7 H 6mg / m 2 1,2- bis (vinylsulfonyl acetamide ) Ethane 22 mg / m ^{2 The} coating solution pH was 6.4. 20 μl of distilled water was dropped on the completed photosensitive sheet, and the pH value after 1 minute at 25 ° C. was measured with a surface electrode.
Met.

<Sensitive Sheets 2 to 9> The photosensitive sheet 1 was prepared in exactly the same manner as the photosensitive sheet 1 except that the dispersion A of the antihalation layer was changed to the dispersions B to I (120 mg / m ² as the dye (II)). -9.

<Photosensitive sheet 10> A photosensitive sheet 1 was prepared in exactly the same manner except that the antihalation layer was changed as follows. Antihalation layer Gelatin 1500 mg / m ² Dispersion E As dye (II) 80 mg / m ² Dispersion J As dye (III) 100 mg / m ² Potassium polystyrene sulfonate 30 mg / m ² Potassium dodecylbenzene sulfonate 8 mg / m ² Proxel The coating solution of 15 mg / m ² 1,2-bis (vinylsulfonylacetamide) ethane 65 mg / m ² was adjusted to pH 5.6 with a 2% phosphoric acid aqueous solution and applied. Dispersion J is a powder of the following dye (III) prepared in the same manner as Dispersion B.

[0053]

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<Photosensitive Sheet 11> A comparative material prepared in exactly the same manner as the photosensitive sheet 1 except that the dye dispersion was removed from the antihalation layer was used as a photosensitive sheet 11.

Each photosensitive sheet was placed in a fresh state and
A sample subjected to a forced moist heat test for 3 days at 80 ° C. and 80% RH was prepared, subjected to gradation exposure with a continuous wedge, and subjected to a negative development treatment.

<Negative Developing Process> The negative developing process is described in US Patent Allen Product.
s Co., Ltd. F-10 deep tank automatic developing machine, general-purpose processing solution for microfilm (FR Chemicals, USA)
(FR-537 developer, manufactured by KK) under the following conditions. The developed sample was measured with a densitometer, and the change in sensitivity at a density of 1.2 after the forced aging test with respect to the fresh sensitivity was summarized in Table 3.

[0057]

[Table 3]

In comparison with the blank test (photosensitive sheet 11), the sensitivity of the photosensitive sheet according to the present invention is lower than that of the blank test (photosensitive sheet 11), but is greatly improved as compared with the comparative example having a large absorbance ratio at 680 nm. .

Example 7 <Preparation of Photosensitive Sheet 7-1> Biaxially stretched thickness 175
Corona discharge treatment was performed on a blue dyed polyethylene terephthalate film having a thickness of μm, and the hydrophobic polymer layer was coated on both sides with a wire bar coater so as to have the following coating amount, and dried at 175 ° C. for 1 minute. (Hydrophobic polymer layer) Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{/ 31/69 0.322g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 4.2 mg / m ^{Second, the} hydrophilic colloid layer was coated on both sides with a wire bar coater so as to have the following coating amount, and dried at 150 ° C. for 1 minute. (Undercoat second layer (hydrophilic colloid layer)) ・ Gelatin 80 mg / m ²・ Polyethyl acrylate 20 mg / m ²・ Dispersion H Dye (II) 11 mg / m ²・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 4 mg / m ² · Proxel 0.3 mg / m ²

On both sides of the above-mentioned undercoat coating material,
A silver halide emulsion layer and a surface protective layer were coated based on the emulsion preparation method and coating formulation described in Example 1 of No. 64936. At this time, the coating amount per one side of the emulsion layer and the surface protective layer was as follows. <Emulsion layer> ・ Amount of coated silver 1.9 g / m ²・ Amount of coated gelatin 1.2 g / m ² <Surface protective layer> ・ Gelatin 0.61 g / m ²・ Dextran (average molecular weight 39,000) 0.61 g / M ² · sodium polyacrylate (average molecular weight: 41,000) 70 mg / m ² · matting agent (average particle size: 3.5 µm) Polymethyl methacrylate / methacrylic acid = 9/1 copolymer 0.06 g / M ²

[0061]

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4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 15.5 mg / m ^{2 The} hardener was 1,2-bis (sulfonylacetamido) ethane at 56 mg / m ² per side. It applied so that it might become.

<Preparation of Photosensitive Sheet 7-2> Photosensitive Sheet 7
-1 was prepared in the same manner as above except that the dispersion H was changed to the dispersion B in the second layer of the undercoating.
And 2. <Preparation of Photosensitive Sheet 7-3> A blank photosensitive sheet 7-3 was prepared in the same manner as in the undercoating second layer of the photosensitive sheet 7-1 except that the dispersion H was removed.

Evaluation of photographic performance Each photosensitive sheet in a fresh state and at 50 ° C. 68%
A solution stored for 5 days under RH conditions was prepared, and a photosensitive sheet was narrowed between a HR-4 screen manufactured by Fuji Photo Film Co., Ltd. and black paper so as to be in close contact with each other.
X-ray exposure was performed through 0 cm, and the following processing was performed. Current image 35 ° C x 6.3 seconds Fixing 31 ° C x 6.7 seconds Squeeze 15 ° C x 4 seconds Drying 60 ° C x 8 seconds Dry-to-dry processing time 29 seconds The developing solution and fixing solution used have the following composition. did. (Developer) Potassium hydroxide 29 g Potassium sulfite 44.2 g Sodium hydrogen carbonate 7.5 g Boric acid 1.0 g Diethylene glycol 12 g Ethylenediaminetetraacetic acid 1.7 g 5-Methylbenzotriazole 0.06 g Hydroquinone 25 g Glacial acetic acid 18 g Triethylene glycol 12 g 5 -Nitroindazole 0.25 g 1-phenyl-3-pyrazolidone glutaraldehyde (50 wt / wt%) 9.86 g Sodium metabisulfite 12.6 g Potassium bromide 3.7 g Add water 1.0 L (fixer solution) ) Ammonium thiosulfate (70 wt / vol%) 200 ml Disodium ethylenediaminetetraacetate dihydrate 0.02 g Sodium sulfite 15 g Boric acid 10 g Sodium hydroxide 6.7 g Glacial acetic acid 15 g Aluminum sulfate 10 g The total amount 1 liter adding an acid (36N) 3.9 g water. (The pH was adjusted to 4.25.) After the treatment, the emulsion layer on the side in close contact with the black paper was completely removed and subjected to sensitometry to determine fog and fog density +0.2.
The sensitivity at a concentration of 5 was measured. As the results are summarized in Table 4, the dye dispersion of the present invention has high sensitivity in Fresh, and after storage under moist heat conditions, the decrease in sensitivity is small and the increase in fog is extremely small. It shows close performance. According to a conventionally known synthesis method, diffusion to an emulsion layer is likely to occur, which tends to cause a decrease in sensitivity and an increase in fog, and the effect of the present invention is apparent.

[0065]

[Table 4]

Example 8 Preparation of Sample 801 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated 127 μm-thick cellulose triacetate film support to prepare Sample 801. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High-boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g (added in dispersion B of dye II of the present invention)

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0. 4 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.1 g Emulsion B silver amount 0.4 g gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C -3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg Ultraviolet absorber U-1 0.01 g Ultraviolet absorber U-2 002 g UV absorber U-5 0.01 g Dye D-1 0.02 g Dye D-5 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling organic solvent Oil-10 .02g

Eighth Layer: Intermediate Layer A silver iodobromide emulsion having a fogged surface and inside (average particle size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver content 0.02 g Gelatin 1. 0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E silver amount 0.1 g Emulsion F silver amount 0.2 g Emulsion G silver amount 0.2 g gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05g Coupler C-8 0.20g Compound Cpd-B 0.03g Compound Cpd-C 10mg Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd- G 0.02 g Compound Cpd-L 0.05 g High boiling organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g

Tenth Layer: Medium-Sensitive Green-Sensitive Emulsion Layer Emulsion G Silver Amount 0.3 g Emulsion H Silver Amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g Compound Cpd-L 0.05 g High boiling organic solvent Oil-2 0.01g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd- K 5 mg Compound Cpd-L 0.05 g High-boiling organic solvent Oil-1 0.02 g High-boiling organic solvent Oil-2 0.02 g

The twelfth layer: the intermediate layer gelatin 0.6 g

Layer 13: Yellow filter layer Yellow colloidal silver Silver content 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High-boiling organic solvent Oil-1 0.01 g Microcrystalline solid of dye E-2 Dispersion 0.05g

Fourteenth layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: Low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.1 g Emulsion M silver amount 0.4 g gelatin 0.9 g coupler C-5 0.3 g coupler C-6 0.1 g Coupler C-10 0.1 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling organic solvent Oil-2 0.1 g

18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g

Nineteenth layer: Second protective layer Colloidal silver Silver content 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.1 g Gelatin 0.4 g

Twentieth layer: Third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1. 5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

To all the emulsion layers, additives F-1 to F-8 were added in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and butyl p-benzoate were added as preservatives and fungicides.

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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A multilayer color photographic material was prepared in exactly the same manner as in Sample 801 except that Dye E-1 in the first antihalation layer of Sample 801 was added with Dispersion H of Dye II of the present invention.
02.

After the silver halide color photographic light-sensitive material prepared as described above was exposed, it was processed according to the following steps. Processing process Time Temperature First development 6 minutes 38 ° C Rinse 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ° C Rinse 4 minutes 38 ° C Stable 1 minute 25 ° C

The composition of each processing solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g sodium sulfite 30 g hydroquinone potassium monosulfonate 20 g potassium carbonate 15 g weight Sodium carbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Add water 1000 mL pH 9 .60 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g ice Acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide.

[Color developing solution] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate / 12 hydrate 36 g Potassium bromide 1.0 g Iodide Potassium 90 mg Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6- Dithiaoctane-1,8-diol 1.0 g Water was added to 1000 ml pH 11.80 The pH was adjusted with hydrochloric acid or potassium hydroxide.

[Preparation Solution] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g sodium sulfite 12 g 1-thioglycerol 0.4 g formaldehyde sodium bisulfite adduct 30 g Water was added to add 1,000 ml, and the pH was 6.20. Adjusted with hydrochloric acid or sodium hydroxide.

[Bleaching Solution] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g The .70 pH was adjusted with hydrochloric acid or sodium hydroxide.

[Fixing Solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to the mixture, and the pH was adjusted with hydrochloric acid or aqueous ammonia.

[Stabilizing Solution] Benzoisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Water was added to the mixture to make 1,000 ml pH 7.0 Samples 801 and 802 Fresh sample and 50 ° C
After exposing and processing the sample stored at 80% RH for 3 days, the density was measured and the change in red sensitivity was evaluated. Fres
By storage under moist heat conditions of 50 ° C. and 80% RH for h,
Sample 801 of the comparative example exhibited a sensitivity decrease of 0.20, whereas sample 802 using the dispersion of the present invention exhibited a sensitivity of 0.05.
, And a remarkable improvement effect was observed.

[Brief description of the drawings]

FIG. 1 is a graph showing an X-ray diffraction chart of Dye II-.

FIG. 2 is a graph showing an X-ray diffraction chart of Dye II-.

FIG. 3 shows absorption spectra of coating films No. 4-1 and No. 4-5.

[Explanation of symbols]

 2θ indicates the diffraction angle. CPS indicates diffraction intensity. A is the case of No. 4-1. B is the case of No. 4-5.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-92716 (JP, A) JP-A-3-182743 (JP, A) JP-A-3-288842 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03C 1/83

Claims (6)

(57) [Claims] 1. Dispersion of a dye in a silver halide photographic light-sensitive material having, on a support, at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer containing a dispersed solid of the dye (I). In the absorption spectrum based on the dye in the hydrophilic colloid layer containing a solid, 6
A silver halide photographic light-sensitive material, wherein the ratio of the absorbance at 80 nm to the absorbance at 530 nm is 0.50 or less. Embedded image (Where R and R ′ in the above general formula are respectively
Represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an ester group. ) 2. A silver halide photographic light-sensitive material comprising a support having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer containing a dispersed solid of the dye (I). the diffraction angle 2θ of X-ray diffraction)
The first-order diffraction intensity and the diffraction angle 2θ at 26 to 27 degrees are
A silver halide photographic light-sensitive material, wherein the ratio of the second-order diffraction intensity at 14 degrees is 1.30 or less. 3. A silver halide photographic light-sensitive material, wherein the dye (I) according to claim 1 or 2 is obtained by a molecular alignment promoting treatment. 4. Dye (I) according to claim 1 and 2
Is the following dye (II): Embedded image 5. A silver halide photographic material containing the dispersed solid of the dye (I) according to claim 1 or 2, wherein the dispersed solid of the dye (I) is located between the support and the silver halide emulsion layer. A silver halide photographic light-sensitive material. 6. The silver halide photographic light-sensitive material according to claim 5, wherein the layer containing the dye (I) -dispersed solid is between the support and the silver halide emulsion layer, and the hydrophilic colloid of the dye layer is provided. A silver halide photographic light-sensitive material, characterized in that the coating amount of is 0.5 g / m ² or less per side.