JP2001166425A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having good light resistance and to provide a silver halide photographic sensitive material less liable to cause image blurring even after storage, less liable to sweat even after storage and excellent in deposition resistance in production. SOLUTION: Each of the silver halide photographic sensitive materials contains a specified UV absorber for formula 1 or 2. In the formulae 1 and 2, X is -O-, -S- or -N(R3)CO-; L1 is a divalent combining group; L2 is an n-valent combining group; R1 and R2 are each H, halogen, alkyl, alkoxy, thioalkyl or aryl; R3 is H or alkyl; and (n) is an integer of 2-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent light fastness of a formed image.

[0002]

2. Description of the Related Art Silver halide light-sensitive materials are widely used because of their excellent gradation and high sensitivity. Although various performances are required for silver halide photographic materials, light fastness (light fastness) of a formed image is also an important item.

Various methods have been proposed for improving the light fastness of silver halide photographic materials, but the addition of an ultraviolet absorber is one of the effective methods.

[0004] UV absorbers are generally required to have the following properties. 1) It has substantially no absorption in the visible light region. 2) It does not affect other performances such as images. 3) It has a high ultraviolet absorption capacity. Also, for the purpose of suppressing the effects of long-time light irradiation. 4) The compound itself has high light fastness. However, when it is added to a silver halide photographic material, it must be added to an extremely thin layer formed of a hydrophilic binder. For example, even if an ultraviolet absorber having these properties is used, adding a large amount of the ultraviolet absorber to improve the light resistance may cause precipitation of crystals after storage of the ultraviolet absorber over time during production, resulting in a production yield. There is a problem that large troubles are likely to occur in the manufacturing process, such as deterioration of the surface, unevenness of the surface, and defects. Light resistance was also insufficient.

[0005] Therefore, there has been proposed a method for improving the problem of trouble in the production process due to the crystal precipitation. For example, a method in which two kinds of ultraviolet absorbers are used in combination for improvement is described in JP-B-48-5496 and JP-B-48-30493.
No. 48-41572, JP-A-53-85425.
And Japanese Patent Application Laid-Open No. 4-1748.
The present inventor studied these methods and confirmed that the problem caused by precipitation at the time of production could be improved, but it was still insufficient. There is also a problem of a phenomenon in which an oily component appears on the sample surface due to heat or humidity when stored over time (hereinafter referred to as sweating). Light resistance was also insufficient.

[0006]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having excellent light fastness.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in precipitation resistance during production and excellent in light resistance.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which is less likely to cause perspiration even when stored for a long time and has excellent light fastness.

[0009]

The object of the present invention has been attained by the following constitutions.

(1) A silver halide photographic material comprising at least one compound represented by the following general formula (1) or (2).

[0011]

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Wherein X is -O-, -S-, -N
(R ₃ ) CO—, L ₁ represents a divalent linking group,
₂ represents an n-valent linking group; R ₁ and R ₂ represent a hydrogen atom, a halogen, an alkyl group, an alkoxy group, a thioalkyl group,
Represents an aryl group, R ₃ represents a hydrogen atom or an alkyl group, and n represents an integer of 2 to 4.

(2) A silver halide photographic material comprising at least one compound represented by the following general formula (3).

[0014]

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In the formula, R ₁ , R ₂ , X, L ₂ , and n each represent a group having the same meaning as in the above formulas (1) and (2).

(3) A silver halide photographic material comprising at least one compound represented by the following general formula (4).

[0017]

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In the formula, R ₁ , R ₂ , X and n each represent a group having the same meaning as in the above formulas (1) and (2), and A represents Si
Represents a contained group.

(4) A silver halide photographic material characterized by containing an ultraviolet absorber having a molecular weight of 1,000 or more and having 3 to 5 benzotriazole groups in the molecule.

That is, the present inventor has found that a silver halide photographic light-sensitive material using a specific ultraviolet absorber can provide a silver halide photographic light-sensitive material having good light fastness. Further, they have found that a silver halide photographic light-sensitive material having good resistance to deterioration in production yield, image bleeding resistance, and perspiration resistance due to storage over time can be provided, and the present invention has been accomplished.

Hereinafter, the present invention will be described in detail. The compound represented by the general formula (1) or (2) according to claim 1 will be described. In the general formula (1) or (2), preferred examples of the divalent linking group represented by L ₁ include ethylene, trimethylene, tetramethylene, and propylene. Most preferably, it is ethylene.

Typical examples of the n-valent linking group represented by L ₂ include the following.

[0023]

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Of these, preferred is -CH ₂ CH ₂
-. R ₁ and R ₂ represent a hydrogen atom, a halogen, an alkyl group, an alkoxy group, a thioalkyl group, or an aryl group. Examples of the alkyl group include a methyl group, an ethyl group,
sec-butyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the thioalkyl group include an n-octylthio group. Examples of the aryl group include a phenyl group.

R ₃ represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group and an ethyl group.

N represents an integer of 2 to 4, preferably 2 or 3. Specific examples of the compound represented by formula (1) or (2) are shown below, but the invention is not limited thereto.

[0027]

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[0028]

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Next, the compound represented by formula (3) according to the second aspect of the present invention will be described. In the general formula (3), R ₁ , R ₂ , X, L ₂ and n each represent a group having the same meaning as in the general formulas (1) and (2). Hereinafter, specific examples of the compound represented by Formula (3) are shown, but the invention is not limited thereto.

[0030]

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Next, the compound represented by formula (4) according to the third aspect of the present invention will be described. In the general formula (4), R ₁ , R ₂ , X and n each represent a group having the same meaning as in the general formulas (1) and (2), and A represents a Si-containing group.

[0032]

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And the like. Hereinafter, specific compound examples of the compound represented by the general formula (4) are shown, but the invention is not limited thereto.

[0034]

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Next, according to the invention of claim 4, the molecular weight of 1,
An ultraviolet absorber having a molecular weight of 000 or more and having 3 to 5 benzotriazole groups in the molecule will be described.

As the above compounds, there are also oligomers having a low degree of polymerization, which are copolymers of a vinyl monomer having a benzotriazole group linked thereto and another vinyl monomer. However, it is difficult to polymerize a vinyl monomer linked with a benzotriazole group, or when polymerized, the molecular weight becomes too large,
As a result, the content ratio of the benzotriazole group was reduced. Therefore, it is not a polymer, and has a molecular weight of 1,000 to 5,
A 000 benzotriazole multimer is preferred.

Examples of the compounds include the above-mentioned compound examples 1-4,
3-5, 4-2, 4-3 and the like.

In the present invention, the term "ultraviolet absorber" means a compound having a maximum absorption wavelength at 400 nm or less and having a molecular extinction coefficient of 10,000 or more in chloroform.

The compounds according to the first to fourth aspects of the present invention are added to a silver halide photographic material as an ultraviolet absorber and may be added to any of a photosensitive layer and a non-photosensitive layer. It is added to the photosensitive layer. Among the non-photosensitive layers, it is more preferable that the non-photosensitive layer is added to the non-photosensitive layer adjacent to the photosensitive layer farthest from the support.

The ultraviolet absorbent according to the present invention may be used in combination with another ultraviolet absorbent.

In the present invention, the total amount of the ultraviolet absorber added to the silver halide photographic light-sensitive material (the ultraviolet absorber according to the present invention and another ultraviolet absorber) is 0.3 to 0.3.
1.0 g / m ^2, more preferably 0.3 to 0.9 g / m ² ,
More preferably, it is 0.3 to 0.8 g / m ² , most preferably 0.3 to 0.7 g / m ² .

Examples of the synthesis of representative compounds according to the present invention are shown below. Synthesis Example of Exemplified Compound 1-1 In 350 ml of toluene, 2- (2'-hydroxy-
27 g of 4'-hydroxyethyloxy) -benzotriazole and 10 g of succinic anhydride were added, and the mixture was refluxed for 3 hours, and 50 ml of the solvent was distilled off under reduced pressure. After cooling,
27 g of 2- (2'-hydroxy-4'-hydroxyethyloxy) -benzotriazole was added and dissolved, 200 g of DCC was added in 30 minutes, and the mixture was further refluxed for 2 hours. Recrystallization was performed by adding 150 ml of acetonitrile to obtain 40 g of the desired product (yield 62%, white crystals).

In addition, the compounds of the present invention can be synthesized by applying known methods such as US Pat. Nos. 5,739,348, 5,683,861, and 5,670,654. .

The composition of the silver halide photographic emulsion used in the present invention may be any halide composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide and the like. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

In order to obtain a silver halide emulsion used in the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions.

The composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion used in the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt.
Examples thereof include Group 10 metals, Group 12 transition metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be cyanide ion, thiocyanate ion, cyanate ion, isothiocyanate ion, chloride ion, bromide ion, iodide ion, or the like. Examples include nitrate ion, carbonyl, ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion and bromide ion are preferable.

In order to incorporate a heavy metal ion into the silver halide emulsion used in the present invention, the heavy metal compound is added before forming silver halide grains, during forming silver halide grains,
It may be added at any place in each step during physical ripening after the formation of silver halide grains. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol to 1 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ mol.
Mol to 5.times.10.sup.- ⁵ mol is preferred.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,22
5,666, JP-A-55-26589, and JP-B-55-55.
No. 42737 and the Journal of Photographic Science (J. Photogr. Sc.
i. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Further, particles having a twin plane may be used.

The silver halide grains used in the present invention are:
Although grains having a single shape are preferably used, it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 in consideration of other photographic properties such as rapid processing and sensitivity.
μm, and more preferably in the range of 0.2 to 1.0 μm.

The particle size can be measured using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of not more than 0.22, more preferably not more than 0.15, particularly preferably not more than 0.15. That is, two or more monodisperse emulsions having a coefficient of 0.15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the present invention is
It may be obtained by any of an acidic method, a neutral method, and an ammonia method. The silver halide grains may be grown at a time, or may be grown after seed grains are formed. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Furthermore, the simultaneous mixing method 1
The pAg controlled double jet method described in JP-A-54-48521 can also be used.

In addition, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

Further, a silver halide solvent such as thioether may be used if necessary. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the present invention is:
A sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer can be used in combination.

As the chalcogen sensitizer applied to the silver halide emulsion used in the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used.
Sulfur sensitizers are preferred. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like, but is preferably 5 × 10 ^{-10 to} 5 × 10 -5 per mol of the silver halide. In the range of ^10-5 mol, preferably 5
The range is preferably from × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 10
^-8 mol.

The chemical sensitization of the silver halide emulsion used in the present invention may be a reduction sensitization.

The silver halide emulsion used in the present invention can prevent fog generated during the process of preparing a silver halide photographic material, reduce performance fluctuations during storage,
Known antifoggants and stabilizers can be used for the purpose of preventing fogging during development.

Examples of preferred compounds which can be used for such purposes are described in JP-A-2-14636.
Compounds represented by the general formula (II) described in the lower column of the page can be mentioned, and more preferable specific compounds are (IIa-1) to (IIa) described on page 8 of the publication.
a-8), the compounds of (IIb-1) to (IIb-7), and 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.

When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, and is preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻ mol. ³ moles are more preferred. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 mol per mol of silver halide is used.
Preferably the amount of about × 10 ^-6 mol to 1 × 10 ^-1 mol, 1
More preferably, it is from × 10 ⁻⁵ mol to 1 × 10 ⁻² mol. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

The silver halide photographic light-sensitive material of the present invention includes:
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, dyes having absorption in the visible region include AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared absorbing dyes include general formulas (I) and (II) described in the lower left column of page 2 of JP-A-1-280750. , (III) have preferred spectral characteristics, have no effect on the photographic characteristics of the silver halide photographic emulsion, and are free from contamination by residual color.
As specific examples of preferred compounds, the exemplified compounds (1) to (4) listed in the lower left column of page 3 to the lower left column of page 5 of the publication are referred to.
5).

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferably 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention because whiteness can be improved. Preferred examples of the compound include compounds represented by the general formula described in JP-A-2-232652.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, a halogen spectrally sensitized to a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any of known compounds can be used, and as the blue-sensitive sensitizing dye, JP-A-3-251840 28 BS-1 described on the page
To 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-29 described on page 29 of the same publication are used.
8 is preferably used. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515.
Compounds S-1 to S-1 described on pages 15 to 17
7 is preferably used in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

As the coupler used in the silver halide photographic light-sensitive material of the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Although any compound obtained can be used, particularly typical ones are a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 6
Representatively, a magenta dye-forming coupler having a spectral absorption maximum wavelength at 00 nm and a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm are representative.

Cyan couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include compounds represented by formulas (C-I) and (C-II) described in JP-A-4-114154, page 5, lower left column. And a coupler represented by the following formula: Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column in the same publication.

As magenta couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention, general formulas (MI) and (M-II) described in JP-A-4-114154, page 4, upper right column. And a coupler represented by the following formula: Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Preferred from among the magenta couplers is a coupler represented by the general formula described in the publication 4 pages, right upper column (M-I), of which, R _M of the formula (M-I) is 3 A coupler which is a lower alkyl group is particularly preferable because of its excellent light resistance. MC-8 to MC-1 described in the upper column of page 5 of the gazette
No. 1 is preferable because it is excellent in reproducing colors from blue to purple and red, and is also excellent in detail description.

As the yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, a coupler represented by the general formula (YI) described in the upper right column of page 3 of JP-A-4-114154 can be used. Can be mentioned. Specific compounds are listed in the lower left column of page 3 of the publication, and
Those described as C-1 to YC-9 can be mentioned. Among them, R _Y 1 of the general formula [Y-1] of the publication
Wherein R is an alkoxy group or JP-A-6-673.
The coupler represented by the general formula [I] described in JP-A-88-88 is preferable because it can reproduce yellow having a preferable color tone. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154.
And No. 6 described in JP-A-6-67388, pages 13-14. Compounds represented by (1) to (47) can be mentioned. Further, the most preferred compound is disclosed in
The compound represented by General Formula [Y-1] described on page 1 of JP-A-81847 and pages 11 to 17 of the same publication.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material of the present invention, the boiling point is usually 15 points.
It is dissolved in a water-insoluble high-boiling organic solvent of 0 ° C. or more, if necessary, in combination with a low-boiling and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. . 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 or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, and phosphates such as trioctyl phthalate, Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 described in JP-A-64-26854.
A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution after the addition are preferably shorter.
The time is preferably within 3 hours, more preferably within 3 hours and within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541 and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. Amine compounds represented by the general formula A described in JP-A-64-90445,
The metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP 182741 are particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-) described in the lower left column of page 10 of the same publication are disclosed. Compounds such as 1) can be used. In addition to this, U.S. Pat.
Can be used.

In the silver halide light-sensitive material of the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056,
Compounds II-1 to II-14 described on page 4 and compound 1 described on page 17 are exemplified.

The silver halide photographic light-sensitive material of the present invention includes
It is advantageous to use gelatin as a binder, but if necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, a homopolymer or a copolymer A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener or a carboxy active hardener alone or in combination. JP-A-61-249054 and 61-245
It is preferable to use the compound described in JP-A-153-153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the silver halide photographic light-sensitive material of the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, A vinyl sheet, a polypropylene that may contain a white pigment, a polyethylene terephthalate support, baryta paper, or the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, 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 silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support was 13% by mass in order to improve sharpness.
The above is preferred, and more preferably 15% by mass.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support used in the present invention 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 as a coefficient of variation described in the above-mentioned publication,
More preferably, it is 15 or less.

The center surface average roughness (SRa) of the support is usually 0.15 μm or less, more preferably 0.12 μm or less, because excellent effects can be obtained in terms of glossiness, and it is more preferable.

Ultramarine blue, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve the whiteness. It is preferred to add a trace amount of a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoating (adhesion of the support surface, charging, etc.). Or one or more subbing layers for improving the anti-static property, dimensional stability, friction resistance, hardness, anti-halation property, frictional properties and / or other properties). .

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the silver halide photographic light-sensitive material of the present invention, an image recorded on a negative is optically imaged on a silver halide photographic light-sensitive material to be printed. The image may be converted into digital information, then formed into an image on a CRT (cathode ray tube), and the image may be formed on a silver halide photographic material to be printed. The printing may be performed, or the printing may be performed by changing the intensity of the laser beam based on the digital information and scanning.

The present invention is preferably applied to a light-sensitive material in which the developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material having a reflective support.

As the color developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (methanesulfonamido) ethyl) aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developing agent is used in a color developing solution, and the color developing solution can be used in an arbitrary pH range. It is preferably 13.0, and more preferably used in the range of pH 9.8 to 12.0.

The processing temperature for color development used in the present invention is preferably 35 ° C. to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high, and the processing is preferably performed at 37 ° C to 60 ° C.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers disposed in a processing tank, or a belt. An endless belt system that fixes and transports the photosensitive material may be used,
A processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and a photosensitive material is transported. A spray method is used to spray the processing liquid. A web method is used to contact a carrier impregnated with the processing liquid. Alternatively, a method using a viscous treatment liquid may be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. The processing agent is added in the form of
35 is most preferred.

[0107]

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

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was applied, a reflective polyethylene support was prepared by laminating molten polyethylene containing a surface-treated anatase type titanium oxide dispersed at a content of 15% by mass. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a silver halide photographic material. As a hardener, H-
1, H-2, F-1 was used as a preservative.

[0109]

[Table 1]

[0110]

[Table 2]

DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6 -Hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecyl Hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl hydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone Image stabilizer A: P -T-octylphenol

[0112]

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[0113]

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[0114]

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[0115]

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(Preparation of Blue-Sensitive Silver Halide Emulsion)
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (solution A) and (solution B) and (C solution) and (D
Liquid), the average particle size was 0.64 μm and the variation coefficient of the particle size distribution was 0.0
7. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-1B was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a thickness of 0.08 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole SS-1 was added in an amount of 2.0 × 10 ⁻³ per mol of silver halide.

[0124]

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[0125] The sample thus prepared was used as the sample 10
Let it be 1. Next, each sample was prepared in the same manner except that the ultraviolet absorbers added to the sixth layer and the fourth layer were changed to the combinations shown in Table 3.

In the preparation of each sample, however, the coating solution for each layer was applied after storage at 40 ° C. for 5 hours in order to cope with mass production.

Each of the samples thus prepared was exposed to a blue light wedge according to a conventional method, and then subjected to a developing process in the following developing process to produce a color print having a yellow wedge image.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. Is pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fixing solution tank replenisher and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank liquid and replenisher o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make up to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Each sample obtained in this manner was subjected to 85
After storage for 2 weeks at 60 ° C. and a relative humidity of 60%, the perspiration resistance was visually observed by ten observers according to the following criteria in a 10-point scale, and the average score was used as a measure of the perspiration resistance.

Evaluation criteria for perspiration resistance: Large number of large oil components on the surface: 1 Oil component generated on the surface: 5 Slight generation of oil component on the surface: 8 No perspiration on the surface: 10 In addition, each sample after the above two-week storage The light resistance of a portion having a yellow reflection density of 1.0 was measured by using an underglass outdoor exposure table, and the red light reflection density before and after fading was measured when the sun was exposed to sunlight for 90 days. The fading rate due to light was determined as follows.

Fading rate (%) = 100 × (D−D ₀ ) / D ₀ D ₀ = reflection density before light fading D = reflection density after light fading Table 3 shows the results thus obtained.

[0135]

[Table 3]

[0136]

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As is evident from Table 3, the sample of the present invention has better light resistance than the comparative sample. Also, it can be seen that the sweat resistance is excellent.

The total amount of the ultraviolet absorber added was 1.00.
from the sample 108 is g / m ^2, more of the sample 107 is 0.75 g / m ² is preferably greater than the effect of the present invention.

Example 2 The same processing as in Example 1 was changed as described below.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Drying 60 ８０80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3 5.5 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30g 30g Add water to make the total volume 1 liter, PH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution tank solution and replenisher solution Tank solution Replenisher solution diethylenetriaminepentaacetate ammonium ferric dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, use potassium carbonate or glacial acetic acid to make the tank solution pH = 7.0, and make up the replenisher solution pH = 6.
Adjust to 5.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

As a result of evaluation in the same manner as in Example 1, it was found that the sample of the present invention was superior to the comparative sample.

Example 3 In Example 1, an automatic developing machine, N manufactured by Konica Corporation was used.
PS-868J, ECOJET-P as processing chemical
And a running process was performed according to the process name CPK-2-J1. As a result of evaluation in the same manner as in Example 1, it was found that the sample of the present invention was superior to the comparative sample.

[0146]

As demonstrated in the Examples, the photographic dispersion containing an ultraviolet absorbent according to the present invention and the silver halide photographic light-sensitive material containing the ultraviolet absorbent exhibit little image bleeding even when stored over time. Even when stored for a long period of time, there is little generation of perspiration, and it has an effect of being excellent in precipitation resistance during production.

Claims (4)

[Claims] 1. A silver halide photographic material comprising at least one compound represented by the following general formula (1) or (2). Embedded image [In the formula, X, -O -, - S -, - N represents the (R ₃₎ CO-, L ₁ represents a divalent linking group, L ₂ represents an n-valent linking group, R ₁ and R _{2 each} represent a hydrogen atom, a halogen, an alkyl group, an alkoxy group, a thioalkyl group, or an aryl group; R ₃ represents a hydrogen atom or an alkyl group;
Represents an integer of from 4 to 4. ] 2. A silver halide photographic material comprising at least one compound represented by the following general formula (3). Embedded image [In the formula, R ₁ , R ₂ , X, L ₂ , and n each represent a group having the same meaning as in the general formulas (1) and (2). ] 3. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (4). Embedded image [Wherein, R ₁ , R ₂ , X, and n each represent a group having the same meaning as in the general formulas (1) and (2), and A represents a Si-containing group. ] 4. A silver halide photographic material comprising a UV absorber having a molecular weight of 1,000 or more and having 3 to 5 benzotriazole groups in the molecule.