JPH05165144A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce deterioration of lightfastness and increase of stains even at the time of rapid processing and to enhance background whiteness by incorporating specified silver halide grains in at least one of emulsion layers and a specified compound in at least one layer. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers contains the silver halide grains having a silver chloride content of >=90mol%, and at least one layer contains the compound represented by formula I in which each of R1 and R2 is a substituent and at least one of them is alkoxy or aryloxy, but when R1 is alkoxy, R1 is eliminated on the meta position to the OH group; X is halogen; and each of l, m, and n is an integer of 0-4 and l+m=>=1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a silver halide photographic light-sensitive material suitable for rapid processing, excellent in light stability of dye images, less in the occurrence of stain by light, excellent in static resistance, whiteness and color reproducibility. Regarding materials.

[0002]

BACKGROUND OF THE INVENTION In recent years, high image quality in the industry
A silver halide photographic light-sensitive material that can be processed rapidly is desired.

In the development processing of silver halide photographic light-sensitive materials, continuous processing is usually carried out by an automatic developing machine provided at each developing station. It is required to develop and return it to the user within the day, and recently it is even required to return it within a few hours from the reception desk, and the need for rapid processing is increasing. ing. Furthermore, shortening the processing time improves production efficiency,
Development of rapid processing and high-speed printing is urgently required because cost reduction can be achieved.

In order to achieve rapid processing, a light-sensitive material and a processing solution are approached from two sides. Regarding color development processing, attempts have been made to increase the temperature, increase the pH, increase the concentration of the color developing agent, and the like, and it is also known to add an additive such as a development accelerator. As the development accelerator, 1-phenyl-3-pyrazolidone described in British Patent 811,185, N-methyl-p-aminophenol described in U.S. Pat.No. 2,417,514, N, N, N described in JP-A-50-15554. ′, N′-Tetramethyl
-p-phenylenediamine and the like. However, these methods do not achieve sufficient swiftness, and often cause performance deterioration such as increased fog.

On the other hand, it is known that the shape, size and composition of the silver halide grains of the silver halide emulsion used for the light-sensitive material have a great influence on the development speed and the like, and particularly the halogen composition has a great influence. It has been found that particularly high development rates are exhibited when high chloride silver halide is used.

When such rapid processing is carried out, processing liquid components such as development tend to remain in the photosensitive material, resulting in deterioration of light resistance and increase in yellow coloring due to light, which is a problem. In particular, the light yellow coloring becomes more remarkable as the speed of the treatment is increased. In addition, static light fog occurs in high-speed printers.
Although it is possible to improve the light resistance of a color image and reduce yellow coloring with an ultraviolet absorber, conventional ultraviolet absorbers are not sufficient, and the effect of preventing light stain particularly in rapid processing is small, and a large amount of addition is required. It was necessary and caused deterioration of whiteness and deterioration of sweat resistance.

Therefore, it has been desired to propose a method for improving the light resistance in rapid processing and improving the light yellow stain.

As a result of various studies by the inventors of the present invention, the silver halide photographic light-sensitive material not only has good light resistance even in rapid processing and has little light stain, and has improved static light fog resistance. The material was found and the present invention was achieved.

[0009]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide photographic light-sensitive material which is free from deterioration of light resistance and increase in stain even when the light-sensitive material is rapidly processed.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having excellent light resistance and good whiteness.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having improved static light fog resistance and color reproducibility in a high speed printer and rapid processing.

[0012]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer is provided. A silver halide photographic light-sensitive material containing silver halide grains having a silver chloride content of 90 mol% or more, and at least one layer containing a compound represented by the following general formula (I):

[0013]

[Chemical 3]

In the formula, R ₁ and R ₂ represent a substituent. However, R ₁
At least one of R ₂ and R ₂ represents an alkoxy group or an aryloxy group. Moreover, the case where R ₁ is an alkoxy group and is in the meta position to the hydroxy group is excluded. X represents a halogen atom. l, m and n represent an integer of 0-4. However, the sum of l and m is 1 or more.

In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one light-sensitive silver halide emulsion layer has a silver chloride content of 90 mol%. It is achieved by a silver halide photographic light-sensitive material containing the above silver halide grains and at least one layer containing a compound represented by the following general formula (II).

[0016]

[Chemical 4]

In the formula, R ₁ and R ₂ represent a substituent. X and Y
Represents a halogen atom. n represents an integer of 1 to 4, l,
m and p show the integer of 0-4.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The general formula (I) according to the present invention.
In the compound represented by, the substituents represented by R ₁ and R ₂ include an alkyl group (eg, methyl group, ethyl group, hexyl group, octyl group), aryl group (eg, phenyl group), alkoxy group (eg, methoxy group). Group, butoxy group,
Hexyloxy group, octoxy group), aryloxy group (for example, phenoxy group) and the like. These groups may be branched or may be substituted with other substituents. However, at least one of R ₁ and R ₂ represents an alkoxy group or an aryloxy group. Moreover, the case where R ₁ is an alkoxy group and is in the meta position to the hydroxy group is excluded. X
Represents a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). l, m and n represent an integer of 0-4.
However, the sum of l and m is 1 or more.

Next, examples of typical compounds represented by the general formula (I) according to the present invention will be given.

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

In the compound represented by the general formula (II) according to the present invention, the substituent represented by R ₁ and R ₂ is an alkyl group (eg, methyl group, ethyl group, hexyl group,
Octyl group), aryl group (eg phenyl group), alkoxy group (eg methoxy group, butoxy group, hexyloxy group, octoxy group), aryloxy group (eg phenoxy group) and the like. X and Y represent a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). n is 1
Is an integer of 4 and l, m and p are integers of 0-4.

Next, examples of typical compounds represented by the general formula (II) according to the present invention will be given.

[0027]

[Chemical 10]

[0028]

[Chemical 11]

The compounds represented by the general formulas (I) and (II) according to the present invention preferably have a spectral absorption maximum wavelength in a solution in ethyl acetate of 340 nm to 370 nm and a molecular absorption at the absorption maximum wavelength. Coefficient is 18000l ・ cm ^-1・ mol ^-1
It is above, and more preferably, the spectral absorption maximum wavelength is 34
The molecular extinction coefficient is 4 nm to 360 nm and the spectral absorption maximum wavelength is 20000 l · cm ⁻¹ · mol ⁻¹ or more. More preferably, the spectral absorption maximum wavelength is 346 nm ~ 355 nm and the molecular extinction coefficient at the spectral absorption maximum wavelength is 24000 lcm ^-1 mol
^-1 or more. Furthermore, the molecular extinction coefficient at 390 nm is 2
000l ・ cm ^-1・ mol ^-1 or less, and further 1000l ・ cm ^-1・ mol
^It is preferably ^-1 or less. Therefore, the preferable spectral absorption characteristic is that the spectral absorption maximum wavelength is 344 nm to 360 nm, and the molecular absorption coefficient at the spectral absorption maximum wavelength is 20000 lcm ^-1 mol ^-1.
Above, and the molecular extinction coefficient at 390 nm is 2000 lcm
^-1 · mol ^-1 or less. Most preferably, the spectral absorption maximum wavelength is 346 nm ~ 355 nm and the molecular absorption coefficient at the spectral absorption maximum wavelength is 24000 lcm ^-1 mol ^-1 or more and 390 nm
Has a molecular extinction coefficient of 2000 l · cm ⁻¹ · mol ⁻¹ or less.

The compounds represented by the general formulas (I) and (II) can be used in combination with other benzotriazole type ultraviolet absorbers. Further, the compound of the general formula (I) and the general formula (I
The compound of I) can also be used in combination.

The compounds represented by formulas (I) and (II) may be added to either the photosensitive layer or the non-photosensitive layer, but are preferably added to at least the non-photosensitive layer. It is preferably added at least to the non-photosensitive layer on the side of the photosensitive layer farthest from the support opposite to the support. The amount added is not limited, but is preferably 0.05 to 15 g / m ² , and more preferably 0.1 to 5 g / m ² .

Silver halide grains having a silver chloride content of 90 mol% or more are used in at least one of the light-sensitive silver halide emulsion layers of the present invention. Preferably, the silver halide grains have a silver chloride content of 90 mol% or more, a silver bromide content of less than 10 mol%, and a silver iodide content of 0.5 mol% or less. More preferably, it is a silver chlorobromide having a silver bromide content of 0.2 to 2 mol%.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 10 mol% or less.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, chloride occupying all silver halide grains contained in the emulsion layer. The proportion of silver halide grains having a silver content of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grain of the present invention may be uniform from the inside to the outside of the grain,
The composition inside and outside the particle may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grain of the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. It is a range. The particle size is
It can be measured by various methods generally used in the art. A typical method is Loveland's "particle size analysis method" (ASTM Symposium
On Light Microscopy, 1955, 94-122
Page) or "The Theory of Photographic Process" (Mith and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966)).

This particle size can be measured by using the projected area of the particle or a direct approximation. If the particles are of substantially uniform shape, the particle distribution can be fairly accurately expressed as either diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

[0039]

[Equation 1]

Here, ri represents the particle size of each particle and ni represents the number thereof. The term "particle size" used herein means the diameter of a spherical silver halide grain, and the diameter of a cube or a non-spherical grain when the projected image is converted into a circular image of the same area. ..

The silver halide grains used in the emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammoniacal method. The particles may be grown at one time,
The seed particles may be grown and then grown. The method of forming seed particles and the method of growing seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any of a forward mixing method, a back mixing method, a double mixing method, or a combination thereof, but the double mixing method is preferable. Further, the pAg-controlled double jet method described in JP-A-54-48521 can be used as one form of the simultaneous mixing method.

If necessary, a silver halide solvent such as thioether may be used.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP
55-26589, Japanese Patent Publication No. 55-42737, The Journal of Photographic Science (J.Phot
gr.Sci), 21 , 39 (1973) and the like, particles having a shape such as an octahedron, a tetrahedron and a dodecahedron can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The silver halide grains used in the emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt during the grain forming process and / or the growing process. , An iron salt or a complex salt may be used to add a metal ion to the inside of the particle and / or the surface of the particle so that the metal ion can be incorporated therein. Nucleus can be imparted.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed.
Alternatively, it may be contained as it is. The removal of the salts can be carried out according to the method described in Research Disclosure 17643.

The silver halide grain used in the emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains whose latent image is mainly formed on the surface are preferable.

The emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method using a selenium compound, the reduction sensitization method using a reducing substance, the noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

In the present invention, a chalcogen sensitizer can be used as the chemical sensitizer. The chalcogen sensitizer is a general term for a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer. For photographic use, the sulfur sensitizer and the selenium sensitizer are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Rhodanine can be mentioned. Others, U.S. Patent 1,574,944
No. 2, No. 2,410,689, No. 2,278,947, No. 2,728,668,
No. 3,501,313, No. 3,656,955, West German application published (OLS)
The sulfur sensitizers described in 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 ^-7 to 10 ^-1 mol per mol of silver halide. A molar amount is preferable.

A selenium sensitizer can be used in place of the sulfur sensitization. As the selenium sensitizer, aliphatic isoselenocyanates such as allyl isoselencyanate, selenoureas, selenoketones, selenoamides, Selenocarboxylates and esters, selenophosphates, diethyl selenide, selenides such as diethyl diselenide can be used, and specific examples thereof are described in U.S. Patents 1,574,944, 1,602,592, and 1,623,499. Have been described.

Further, reduction sensitization can be used together. The reducing agent is not particularly limited, but examples thereof include stannous chloride, thiourea dioxide, hydrazine and polyamine.

A noble metal compound other than gold, such as a palladium compound, can also be used in combination.

The silver halide grains according to the present invention preferably contain a gold compound. As the gold compound preferably used in the present invention, the oxidation number of gold may be +1 or +3, and various gold compounds are used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide and the like. Be done.

The gold compound may be used for sensitizing the silver halide grains, or may be used so as not to substantially contribute to the sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guide, from 10 ^-8 mol per mol of silver halide
It is 10 ^-1 mol, preferably 10 ^-7 mol to 10 ^-2 mol. Further, these compounds may be added at any of the steps of grain formation of silver halide, physical ripening, and completion of chemical ripening.

The emulsion of the present invention can be spectrally sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

The effect of the present invention is that the blue-sensitive silver halide emulsion of the silver halide emulsion has a spectral sensitivity of 400 nm spectral sensitivity / 460.
It can be effectively exhibited when the nm spectral sensitivity ratio is 0.9 or less.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
AI described in Japanese Patent Application No. 2-51124, pages 117-118
The dyes 1 to 11 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are used. It has preferable spectral characteristics, has no influence on the photographic characteristics of the silver halide photographic emulsion, and is free from contamination due to residual color. As specific examples of preferable compounds, the exemplified compounds (1) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication
(45) can be mentioned.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm is formed by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength region of 600 to 750 nm.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (Y-I) described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned.
Specific compounds are described in YC-1 to YC-9 on pages 9 to 11 of the same specification.
Can be mentioned. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce yellow of a preferable color tone.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, there are described general formulas (M-I) and (M-II) described on page 12 of Japanese Patent Application No. 2-234208. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are preferable because they are excellent in the reproduction of colors from blue to purple and red and are also excellent in the detail descriptive power.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Japanese Patent Application No. 2-234208, the general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC-1 on pages 18 to 21 of the specification.
To those described as CC-9 can be mentioned.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used to dissolve and disperse the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic-solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be used. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt-
Butyl acrylamide) and the like.

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{-3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin, etc. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can be used.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer, and further, It is preferable that the content is 13% by weight or more, and 15
More preferably, it is at least wt%. The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention is
It can be measured by the method described in JP-A 2-28640.
When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property and / or other property) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The color-developing agent used in the color-developing solution in the present invention includes known ones widely used in various color photographic processes.

In the present invention, after color development, the processing solution having a bleaching ability is immediately processed, but the processing solution having a bleaching ability may be a processing solution having a fixing ability (so-called bleach-fixing solution).

As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used.

[0077]

EXAMPLES The present invention will now be specifically described with reference to examples, but the embodiments of the present invention are not limited to these.

Example 1 On a paper support having polyethylene laminated on one side thereof and polyethylene containing titanium oxide and a bluing agent laminated on the first layer side of the other side thereof, the constitution shown in Tables 1 to 3 was used. Each layer was coated to prepare a multilayer silver halide color photographic light-sensitive material sample 1. The coating liquid was prepared as follows.

Third layer coating solution 35 g of magenta coupler (MA), anti-staining agent (H
Q-1) 1.0 g and 30 g of high boiling organic solvent (DNP) were dissolved by adding 60 ml of ethyl acetate, and this solution was emulsified and dispersed in 200 ml of 10% gelatin aqueous solution using an ultrasonic homogenizer to prepare a magenta coupler dispersion. ..

This dispersion was mixed with a green-sensitive silver halide emulsion (containing 27 g of silver) prepared under the following conditions to prepare a coating solution for the third layer.

Coating solutions for the other layers were prepared in the same manner as the coating solution for the third layer. Further, the same sample as sample 1 was prepared except that the ultraviolet absorbers of the fourth and sixth layers and the anti-fading agent of the third layer were changed in the combinations shown in Table 4. Hardener is H-
1 and H-2 were used.

H-1 2-4-dichloro-6-hydroxy-1,
3,5-triazine sodium _{H-2 C (CH 2 SO} 2 CH = CH 2) 4 [ preparation method of blue-sensitive silver halide emulsion] The following 2% aqueous solution of gelatin 1000ml was kept to 40 ° C. (A liquid) and (B
Solution) is added simultaneously over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (solution C) and (solution D) are added to pAg =
Simultaneous addition was carried out over 180 minutes while controlling 7.3 and pH = 5.5.

At this time, the control of pAg is disclosed in JP-A-59-45437.
The method described in No. 1 was used, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) NaCl 3.42 g KBr 0.03 g H ₂ O was added and 200 ml (Solution B) AgNO ₃ 10 g H ₂ O was added and 200 ml (Solution C) NaCl 102.7 g KBr 1.0 g H ₂ O was added. 600ml (Solution D) 300g AgNO ₃ 300g H ₂ O was added and after 600ml addition was completed, desalting was performed using 5% aqueous solution of Demol N and 20% magnesium sulfate manufactured by Kao Atlas, and then mixed with aqueous gelatin solution. Thus, a monodisperse cubic emulsion EMP-1 having an average grain size of 0.85 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-A).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer SB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye D-1 5 × 10 ⁻⁴ mol / mol AgX [green Preparation Method of Sensitive Silver Halide Emulsion] (Liquid A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) were changed in the same manner as in EMP-1, except that the average particle size was 0.43 μm.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer SB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye D-2 4.0 × 10 ⁻⁴ mol / mol AgX [red Preparation Method of Sensitive Silver Halide Emulsion] (Liquid A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as in EMP-1, except that the average particle size is 0.50 μm.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-C) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer SB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye D-3 8.0 × 10 ⁻⁵ mol / mol AgX

[0091]

[Chemical 12]

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Chemical 13]

[0096]

[Chemical 14]

[0097]

[Chemical 15]

Photosensitizers (manufactured by Konica Corp.,
After performing optical wedge exposure of green light using KS-7 type), processing was performed according to the following processing steps.

[0099] [Color developer] Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid disodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g potassium carbonate 27 g Water was added to make the total volume 1 l, Adjust to pH = 10.10.

[Bleach-fixing solution] 1 liter of the bleach-fixing solution contains 60 g of ferric ammonium ammonium diamine tetraacetate dihydrate, 3 g of ethylenediamine acetic acid 3 g, ammonium thiosulfate (70% aqueous solution) 100 ml, ammonium sulfite (40% aqueous solution) 27.5 ml. Adjust pH = 5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing Solution] In 1 l of the stabilizing solution, 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetra Acetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Contains ammonium sulfite 3.0 g. Adjust to pH = 7.0 with sulfuric acid or potassium hydroxide.

The processing was carried out after 100 m ² running processing of Sample 1 with an automatic processor whose stabilization was a multi-stage countercurrent system.

After the treatment, the light fastness test of the magenta colored image of each of the obtained samples and the measurement of the light yellow stain and static fog resistance were conducted in the following manner.

[Light resistance test] Each sample was measured for the reflection density of green light before and after fading when exposed to sunlight for 30 days using an underglass outdoor exposure table. The degree of fading due to light (fading rate) was determined as follows.

Fading rate = D-Do / Do × 100 (%) Do = Density before photo-fading D = Density after photo-fading [Measurement of photo-yellow stain] Measure increase in blue-light reflection density of white part in light resistance test did.

[Measurement of Static Light Resistance] Under low conditions, a high speed printer with an E size of 2 million per minute was used as a measure of the static light resistance depending on how many static light fogs are produced per 100 sheets when processed.

The results are shown in Table 4.

[0108]

[Table 4]

* The addition of dinonyl phthalate in the fourth and sixth layers of Sample 9 was 0 g / m ² .

** The silver halide emulsion of Sample 10 is silver chloride.
A 20 mol% silver chlorobromide emulsion was used.

As is clear from Table 4, the samples of the present invention had good light resistance, little light yellow stain generation, and good static resistance. Samples 9, 10, and 12 are more preferable because the static resistance is further improved.

Example 2 The coupler of Sample 1 in Example 1 was replaced with the following Y-2, M-
B and C-3 were changed, and the same sample as Sample 1 was prepared except that the combination of the ultraviolet absorber and the anti-fading agent was changed as shown in Table 5, and the same evaluation as in Example 1 was performed.

The results are shown in Table 5.

[0114]

[Chemical 16]

[0115]

[Chemical 17]

[0116]

[Chemical 18]

[0117]

[Table 5]

As is clear from Table 5, the samples according to the present invention have good light resistance, little light yellow stain generation, and good static resistance.

This effect is first obtained by the configuration of the present invention.

[0120]

EFFECT OF THE INVENTION By using the silver halide photographic light-sensitive material of the present invention, it is suitable for rapid processing, has excellent light stability of a dye image, little stain is generated by light, static resistance, whiteness, and color. A light-sensitive material having excellent reproducibility can be obtained.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer has a silver chloride content of 90. A silver halide photographic light-sensitive material containing at least one mol% of silver halide grains and at least one layer containing a compound represented by the following general formula (I). [Chemical 1] In the formula, R ₁ and R ₂ represent a substituent. However, at least one of R ₁ and R ₂ represents an alkoxy group or an aryloxy group. Moreover, the case where R ₁ is an alkoxy group and is in the meta position to the hydroxy group is excluded. X represents a halogen atom. l,
m and n show the integer of 0-4. However, the sum of l and m is 1 or more. 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer has a silver chloride content of 90. A silver halide photographic light-sensitive material containing at least one mol% of silver halide grains and at least one layer containing a compound represented by the following general formula (II). [Chemical 2] In the formula, R ₁ and R ₂ represent a substituent. X and Y represent a halogen atom. n shows the integer of 1-4, l, m, and p show the integer of 0-4.