JP2843869B2 - Silver halide photographic materials with improved pressure resistance - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved image quality such as sharpness and pressure fog.

[Background of the Invention] A light-sensitive silver halide emulsion differs from luminosity and has properties relating to ultraviolet rays, and this property is a great obstacle depending on the purpose and use of the photosensitive material. By UV exposure,
In order to prevent the deterioration of color reproducibility of color photographs and the reduction of contrast of black-and-white photographs, of course, one of the causes of so-called static marks generated by static electricity during the production of photosensitive materials is ultraviolet rays during discharge. Ultraviolet absorbing compounds are also useful.

UV-absorbing compounds used in photosensitive materials include not only the absorption spectrum characteristics related to the essential function of absorbing ultraviolet light, and the physical characteristics of the extinction coefficient in the required wavelength range, but also when contained in the photosensitive material. However, photographic characteristics such as sensitivity or chemical characteristics that do not adversely affect photographic processing such as production and development are required.

Conventionally, as an ultraviolet absorber, those which are solid at ordinary temperature are generally used in many cases, and a high-boiling solvent is used as a solvent.

For this reason, conventionally, there has been a problem of precipitation of the ultraviolet absorber or a problem of perspiration, which has been a major problem.

As a countermeasure, the present inventors have found that by using an ultraviolet absorber which is liquid at room temperature instead of a solid at room temperature, no precipitation occurs, and a high absorption for dissolving the solid ultraviolet absorber is used. Since no boiling point solvent is used, it has been found that the sweating phenomenon is also improved, the non-photosensitive protective layer can be made thinner, and the sharpness is also improved.

However, these photosensitive materials have a disadvantage that they are susceptible to pressure fog due to contact with other objects during the manufacturing process or during use.

The silver halide photographic light-sensitive material in which the pressure fogging has occurred is significantly deteriorated in terms of image quality. Therefore, if the thickness of the non-photosensitive protective layer is increased, the pressure fog is improved, but the sharpness is reduced and the image quality is deteriorated. Therefore, various countermeasures have been studied for improving pressure fog.

For example, a method of increasing the amount of binder in the emulsion layer, that is, a method of reducing the ratio of silver halide / binder is known, but this method also deteriorates sharpness. Also JP
JP-A-50-56227 describes a method of adding a polymer latex to an emulsion layer, and JP-A-53-13923 describes a method of adding a high-boiling organic solvent to an emulsion layer.

Further, JP-A Nos. 50-116025 and 51-107129 describe a method of adding an iridium salt or a thallium salt when preparing silver halide grains.

In addition, for example, silica, titanium dioxide,
A method of adding fine particles such as polystyrene is known. JP-A-59-72439 discloses a method in which paraffin and polyvinylpyrrolidone are added to a non-photosensitive layer.
No. 19734 describes a method of adding oil droplets and fine particle powder to a protective layer composed of two layers.

However, even if these methods are used, the pressure fog characteristics cannot be sufficiently improved.

Particularly in the case of a silver halide photographic light-sensitive material having a small thickness of the non-photosensitive protective layer, the above-mentioned method is insufficient in the effect of improving pressure fog, and provides good image quality on a screen of sharpness and pressure fog. Could not.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a silver halide photographic material having good image quality in both sharpness and pressure fog.

[Configuration of the invention]

The above object of the present invention is to provide a photographic component layer having at least one photosensitive silver halide emulsion layer on a support,
Silver halide grains contained in at least one of the light-sensitive silver halide emulsion layers have an average silver iodide content higher than the silver iodide content on the outermost surface, and Wherein at least one layer contains at least one ultraviolet absorber which is liquid at room temperature.

Hereinafter, the details of the present invention will be specifically described. First, the liquid ultraviolet absorber used in the present invention (hereinafter, referred to as the liquid ultraviolet absorber of the present invention) will be described.

In the present invention, "liquid at normal temperature" means at 25 ° C.
As defined in "Chemical Encyclopedia (1963) Kyoritsu Publishing", etc.,
It has no constant shape, is fluid, and has a substantially constant volume. Accordingly, the melting point is not limited as long as it has the above properties, but a compound having a melting point of 30 ° C. or lower, particularly preferably 15 ° C. or lower, is preferable.

The liquid ultraviolet absorbent of the present invention may be a single compound or a mixture. As the mixture, those composed of a group of structural isomers can be preferably used. (Structural isomers are described in U.S. Pat. No. 4,587,346.) The liquid ultraviolet absorber of the present invention may have any structure as long as the above conditions are satisfied, but the light fastness of the ultraviolet absorber itself is low. To 2- (2'-) represented by the following general formula [a]:
(Hydroxyphenyl) benzotriazole compounds are preferred.

In the structure of the general formula [a] of the liquid ultraviolet absorber of the present invention, R ₁ represents an alkyl group, and R ₂ represents an alkyl group, an alkoxycarbonylethyl group having 8 carbon atoms or a butoxyethoxycarbonylethyl group. And R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₃ is preferably a hydrogen atom, an alkyl group or an alkoxy group from the viewpoint of fading.

Of the groups represented by R ₁ , R ₂ and R ₃ , at least one is preferably an alkyl group, more preferably at least two are alkyl groups, in order to be liquid at room temperature. .

The alkyl group represented by R ₁ , R ₂ and R ₃ can be any alkyl group, but at least one is preferably a tertiary alkyl group or a secondary alkyl group. In particular, at least one of the alkyl groups represented by R ₁ and R ₂ is preferably a tertiary alkyl group or a secondary alkyl group.

Hereinafter, typical specific examples of the liquid ultraviolet absorber of the present invention will be shown.

The liquid ultraviolet absorbent according to the present invention may contain at least one kind in combination with at least one selected from the ultraviolet absorbents represented by the following general formulas (I) or (II). The use of two or more UV absorbers is acceptable.

[Wherein, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, or an aryl group. R ₃ represents an alkyl group or an allyl group, and A and B each represent -CN, -SO ₂ R ₁₁ , -COOR ₁₂ , -C
A group represented by ONR ₁₃ R ₁₄ or —COR ₁₅ (R ₁₁ and R ₁₂ each represent an alkyl group or an aryl group, and R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group, an aryl group or a piperidino ring, a morpholino Represents an atomic group necessary for forming a ring, a pyrrolidino ring or a piperazino ring.) R ₄ , R ₅ , R ₆ and
R ₇ represents a hydrogen atom or an alkyl group, R ₈ represents an alkyl group or an allyl group, R ₉ and R ₁₀ represent a hydrogen atom, an alkyl group or an aryl group, respectively, and G represents an electron withdrawing group. The amount of the ultraviolet absorber of the present invention is preferably 1
30003000 mg / m ² , more preferably 5-600 mg / m ² .

The ultraviolet absorber of the present invention can be contained in any of the photographic constituent layers, but as conventionally performed,
A layer near the surface, for example, a non-photosensitive layer closest to or adjacent to the support, i.e., an antihalation layer or a back layer,
Further, it is preferable that the compound is contained in a layer furthest from the support and closest to the light source or in a non-photosensitive layer adjacent thereto.

Furthermore, in the case where an ultraviolet absorber is contained on the side closer to the light source side than the blue-sensitive layer, a portion of the ultraviolet light region of the photosensitive layer of the blue-sensitive layer that is as long as possible on the long-wave side and that can sharply shield light is used. Therefore, it is preferable to use the liquid ultraviolet absorber of the present invention in combination with, for example, the ultraviolet absorbers represented by the general formulas [I] and [II].

In order to include the ultraviolet absorber of the present invention in a photographic component layer, if the mixed system of the ultraviolet absorber of the present invention is in a liquid state at normal temperature, it may be used as it is or a low boiling point such as ethyl acetate if necessary. It may be finely dispersed by using a surfactant in a hydrophilic binder such as an aqueous solution of gelatin using a solvent, and this dispersion may be added to a target layer.

In addition, even when the mixed system of these ultraviolet absorbers is in a solid state at room temperature or even in a liquid state, a high boiling organic solvent is used, and if necessary, a low boiling solvent is used. And finely dispersed in the same manner as described above, and can be added to the layer.

When the silver halide emulsion of the present invention contains silver halide grains having an average value of grain size / grain thickness of less than 5, the average silver iodide content (J ₁ ) and the silver iodide content (J ₂ ) of the grain surface determined by X-ray photoelectron spectroscopy satisfy the relationship J ₁ > J ₂ .

The particle size here is the diameter of a circumscribed circle of the plane where the projected area of the particle is the maximum.

 X-ray photoelectron spectroscopy will be described.

Prior to measurement by X-ray photoelectron spectroscopy, the emulsion is pretreated as follows. First, a pronase solution is added to the emulsion, and the mixture is stirred at 40 ° C. for 1 hour to perform gelatin decomposition. Next, the emulsion particles are sedimented by centrifugation, the supernatant is removed, an aqueous solution of pronase is added, and the gelatin is decomposed again under the above conditions. After centrifuging the sample again and removing the supernatant, distilled water is added to redisperse the emulsion particles in distilled water, centrifuged, and the supernatant is removed. After repeating this washing operation three times, the emulsion grains are redispersed in ethanol. This is thinly applied on a mirror-polished silicon wafer to obtain a measurement sample.

For measurement by X-ray photoelectron spectroscopy, for example,
Using PHI ESCA / SAM560 type, apply Mg-Kα
X-ray source voltage 15KV, X-ray source current 40mA, path energy
Perform under the condition of 50 eV.

Ag3d, Br3d, I3d3 / 2 electrons are detected to determine the surface halide composition. The calculation of the composition ratio is performed by the relative sensitivity coefficient method using the integrated intensity of each peak. By using 5.10, 0.81, and 4.592 as the relative sensitivity coefficients for Ag3d, Br3d, and I3d3 / 2, respectively, the composition ratio is given in atomic percent.

When the silver halide emulsion of the present invention contains grains having an average value of grain size / grain thickness of less than 5, the grain size distribution is preferably monodisperse. A monodisperse silver halide emulsion is defined as having a silver halide content within a grain size range of ± 20% of the average grain size being 60% of the total silver halide grain weight.
% Or more, preferably 70% or more, more preferably 80% or more.

Here, the average frequency of the particles having a particle size d _i n _i and di
³ the product n _i × di ³ of is defined as the particle size d _i of when the maximum (three significant figures, the minimum digit is ON 4 discard 5).

The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains having a shape other than spherical.

The particle size can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is zero). Discrimination should be 1000 or more).

Particularly preferred highly monodisperse emulsions of the invention are Is less than 20% of the distribution defined by
It is more preferably at most 15%.

The average particle diameter and the standard deviation of particle diameter herein are to be obtained from d _i of the definition.

When the silver halide emulsion of the present invention is a tabular silver halide emulsion having an average value of grain size / grain thickness of 5 or more, the average silver iodide content (J ₁ ) and the average value (J) of the measured values of the silver iodide content measured on a silver halide crystal 80% or more away from the center with respect to the grain size direction of the silver halide grains using the X-ray microanalysis method. _{When 3} ) is compared, the relationship J ₁ > J ₃ is satisfied.

The X-ray microanalysis method will be described. Silver halide particles are dispersed in an electron microscope observation grid in which an energy dispersive X-ray analyzer is installed in an electron microscope, and the magnification is set so that one particle enters the CRT visual field by cooling with liquid nitrogen, and AgLα, Integrate the intensity of ILα radiation. ILα / AgL
The silver iodide content can be calculated using a calibration curve by preparing the intensity ratio of α in advance.

In a tabular silver halide emulsion having an average value of grain size / grain thickness of 5 or more, the average value of grain size / grain thickness is more preferably 6 or more and 100 or less, particularly preferably 7 or more and 50 or less.

The average silver iodide content in the silver halide grains of the present invention is preferably from 2 to 20 mol%, more preferably from 5 to 15 mol%.
Mol%, particularly preferably 6 to 12 mol%.

The silver iodide content of the grain size / the average value of the thickness is less than 5 is the particle surface by X-ray photoelectron spectroscopy in the silver halide emulsion of the present invention the particles (J ₂₎ is to be 6 to 0 mol It is preferably from 5 to 0 mol%, more preferably from 4 to 0.01 mol%.

According to the measurement by the X-ray microanalysis method in the tabular silver halide emulsion of the present invention in which the average value of the grain size / grain thickness is 5 or more, 80% from the central part in the grain size direction of the silver halide grains. The average value (J ₃ ) of the measured values of the silver iodide content measured on silver halide crystals separated from the above by 6 to 0.
Mol%. It is more preferably 5 to 0 mol%, particularly preferably 4 to 0.01 mol%.

The average thickness of the tabular silver halide grains of the present invention in which the average value of the grain size / the thickness of the grains is 5 or more is preferably 0.5 to 0.01 µm, particularly preferably 0.3 to 0.05 µm. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is preferably from 0.4 to 30 μm, more preferably from 0.5 to 20 μm.
m.

The silver halide emulsion having an average value of grain size / grain thickness of less than 5 preferably used in the present invention is preferably monodisperse, and is preferably a core / shell type. In the tabular silver halide emulsion having an average value of grain size / grain thickness of 5 or more preferably used in the present invention, silver iodide is preferably localized at the center of the grain.

A core / shell type silver halide emulsion having an average value of grain size / grain thickness of less than 5 has a grain structure composed of two or more phases having different silver iodide contents, and has a silver iodide content. Is a phase (referred to as a core) having the highest content of silver halide grains other than the outermost surface layer (referred to as a shell).

The internal phase (core) silver iodide having the highest silver iodide content may preferably have a content of 6 to 45 mol%, more preferably 8 to 40 mol%, particularly preferably 20 to 35 mol%.
Out. The silver iodide content of the outermost surface layer is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.

The ratio of the shell portion of the core / shell type silver halide grains is preferably 10 to 80% by volume, more preferably 15 to 70%.
%, Particularly preferably 20 to 60%.

The ratio of core is 10 to 80% by volume
And more preferably 20 to 50%.

In the present invention, the content difference between the silver iodide core portion having a high silver iodide content and the shell portion having a low silver iodide content is:
It may have a sharp boundary, or may have a continuously changing boundary that is not always apparent.
Further, those having an intermediate phase having a silver iodide content between the core and the shell between the core and the char are also preferably used.

In the case of the core / shell type silver halide grains having the intermediate phase, the volume of the intermediate layer is preferably 5 to 60%, more preferably 20 to 55% of the whole grains. The difference between the silver iodide content of the shell and the intermediate layer, the difference between the silver iodide content of the intermediate layer and the core is preferably 3 mol% or more, and the difference between the silver iodide content of the shell and the core is preferably 6 mol% or more.

The core / shell type silver halide emulsion is preferably silver iodobromide, and the average silver iodide content is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained as long as the effects of the present invention are not impaired.

The core / shell type silver halide emulsion is disclosed in JP-A-59-177535.
Nos. 60-138538, 59-52238, 60-143331
Nos. 60-35726, 60-258536, and 61-14636.

As in the method described in Examples of JP-A-60-138538, the core /
When a shell-type silver halide emulsion is grown starting from seed grains, the silver halide emulsion may have a halogen composition region different from the core at the center of the grain.

In such a case, the halogen composition of the seed grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, and silver chloride. Silver iodobromide or silver bromide of 10 mol% or less is preferred.

The ratio of the seed grains to the total silver halide is 50 by volume.
% Or less, and particularly preferably 10% or less.

The distribution state of silver iodide in the core / shell type silver halide grains can be detected by various physical measurement methods. For example, as described in the Abstracts of the Annual Meeting of 1981, Photographic Society of Japan. It can be examined by measuring luminescence at a low temperature or by X-ray diffraction.

The core / shell type silver halide grains may be normal crystals such as cubic, tetradecahedral, or octahedral, may be composed of tabular twins, or may be a mixture thereof, but are normal crystals. Is preferred.

In a tabular silver halide emulsion having an average value of grain size / grain thickness of 5 or more and silver iodide localized at the center of the grain, the high iodine content phase at the center is the total volume of the grain. Is preferably 80% or less, particularly preferably 60% to 10%. The silver iodide content at the center is preferably from 5 to 45 mol%, particularly preferably from 10 to 40 mol%.
Is preferred. The low iodine content phase surrounding the high iodide content phase at the center (peripheral portion) is composed of silver iodobromide having a silver iodide content of 0 to 10 mol%, more preferably 0.1 to 6.0 mol%. Is preferred.

A tabular silver halide emulsion in which silver iodide is localized at the center can be obtained by the method of growing a spherical seed emulsion disclosed in JP-A-61-14636.

As long as the silver halide grains according to the present invention are used, the effect can be exhibited by using grains having any crystal habit as described above.
Among them, it is preferable to use particles having an aspect ratio of less than 5.

Further, the silver halide grains of the present invention can be used in any photosensitive layer and exhibit an effect, but the effect is more exhibited when the silver halide grain is used in the photosensitive layer farthest from the support, that is, the layer closest to the surface. You.

Various matting agents can be used in the present invention.

Matting agents are well known in the photographic arts,
It can be defined as discontinuous solid particles of an inorganic or inorganic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide,
Titanium oxide, magnesium oxide, aluminum oxide, etc.), alkaline earth metal salts (eg, sulfates and carbonates, specifically barium sulfate, calcium carbonate, magnesium sulfate, etc.), and silver halide grains which do not form an image (A small amount of iodine atom may be added as a halogen component in silver chloride or silver bromide, etc.), glass, and the like.

Examples of the organic matting agent include starch, cellulose ester (eg, cellulose acetate pyropionate, etc.),
Cellulose ether (eg, ethyl cellulose), synthetic resin and the like. Examples of synthetic resins are dispersions of water-insoluble or poorly soluble synthetic polymers, such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, acetic acid). Vinyl), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid A polymer having a combination of the above as a monomer component can be used.

Among them, it is preferable to use a so-called alkali-soluble matting agent.

The term "alkali-soluble matting agent" used herein means any matting agent that can be dissolved in a normal alkaline processing liquid, for example, a developing solution.

Examples of such matting agents include particles of the following high molecular compounds.

1. Copolymer of alkyl methacrylate and methacrylic acid, acrylic acid or itaconic acid.

2. Copolymer of alkyl methacrylate and maleic acid half ester and half amide.

3. Copolymers of styrene with α, β-unsaturated mono- or di-carboxylic acids or half-esters or half-amides of dicarboxylic acids.

4. Graft polymers of methacrylic acid / methyl methacrylate onto a water-soluble maleic anhydride / α-olefin dispersant.

5. Dicarboxylic acid half esters of cellulose derivatives, for example phthalic acid esters of cellulose or hydroxypropylmethylcellulose and hexahydrophthalate.

In general, the amount of monomer is chosen so that the particles are insoluble in water below pH 5 and soluble in water above pH 7.

The polymer particles, 10 to 500 mg / m ² to the normal photographic material,
In particular, it is applied at a rate of 50 to 300 mg / m ² . They are added to the coating solution as an aqueous dispersion.

The particle size of the matting agent is preferably 0.5 to 10 μm, and more preferably 1 to 6 μm.

Examples of the matting agent include MMA: methyl methacrylate MAA: methacrylic acid BMA: ethyl methacrylate MaT1 MMA + MAA (50:50 copolymer particles) particle size 2.9 μm MaT2 MMA + MAA (60:40 copolymer particles) particle size 4.5 μm MaT3 EMA-MMA-MAA (30-30-40 copolymer particles) particle diameter 3.6 μm MaT4 hydroxypropylmethylcellulose hexahydrophthalate particle diameter 2.0 μm MaT5 MMA-MAA (65:15 copolymer particles) particle diameter 3.0 μm.

The location of the matting agent is not particularly limited, but it is desirable that the matting agent be contained in the layer closest to the light source among the constituent layers applied on the support.

Further, a surfactant may be added alone or in a mixture to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsification / dispersion, sensitization and other improvement of photographic properties, and adjustment of the charging line.

These surfactants are natural surfactants such as saponin,
Nonionic surfactants such as alkylene oxide, glycerin and glycidol, higher alkylamines, quaternary ammonium salts, cationic surfactants such as pyridine and other heterocycles, phosphonium and sulfoniums; carboxylic acids, sulfonic acids , Phosphoric acid, sulfate,
Anionic surfactants containing acidic groups such as phosphate esters,
It is divided into amphoteric surfactants such as aminosulfate and phosphates.

From the viewpoint of the antistatic effect, it is desirable to use a nonionic surfactant or a fluorine surfactant.

Preferred fluorinated surfactants have a fluoro-alkyl group, alkenyl group, or aryl group having 4 or more carbon atoms, and examples of the inionic group include anionic groups (sulfonic acid (salt), sulfuric acid (salt), sulfonic acid). (Salt), phosphoric acid (salt)), cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betainic acid (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfammonium salt, An activator containing a phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglycerin group or sorbitan residue) can be mentioned.

These fluorine-containing surfactants are described in JP-A-49-10722,
UK Patent 1,330,356, JP-A-53-84712, JP-A-54-1422
No. 4, No. 50-113221, U.S. Pat.No. 4,335,201, No. 4,34
7,308, British Patent 1,417,915, JP-B-52-26687,
Nos. 57-26719, 59-38573, JP-A-55-149938,
Nos. 54-48520, 54-1224, 58-20235, 57-
Nos. 146248, 58-196544 and British Patent 1,439,402. The layer containing the fluorine-containing surfactant used in this case may be any of the constituent layers of the photographic light-sensitive material, but is preferably added to the protective layer, particularly to the outermost layer. preferable.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The present invention can be applied to all photosensitive materials such as monochrome films, color negative and reversal films, X-ray films, and photographic paper. When used in color light-sensitive materials,
A coupler is used in the emulsion layer of the color photographic material.

Coupling with colored couplers, competing couplers, and oxidized developing agents, which have the effect of correction, further enhances development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, and fog. Compounds that release photographically fragments such as agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

Auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer can be provided on the photosensitive material. In these layers and / or the emulsion layers, dyes which flow out or bleach from the light-sensitive material during the development processing may be contained.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain an image using the light-sensitive material of the present invention, after exposure, a generally known developing process according to the light-sensitive material can be performed.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

In all of the following examples, the amount added in a silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye was represented by the number of moles per mole of silver.

Example 1 A multilayer color photographic element sample 1 was prepared by sequentially forming layers having the following compositions on a triacetyl cellulose film support from the support side.

Sample-1 (Comparative) First layer; Anti-halation layer (HC) Black colloidal silver 0.15 Ultraviolet absorber (UV-1) solid at room temperature 0.20 Colored cyan coupler (CC-1) 0.02 High boiling solvent (OiL-1) 0.20〃 (OiL-2) 0.20 Gelatin 1.6 Second layer; Intermediate layer (IL-1) Gelatin 1.3 Third layer; Low sensitivity red-sensitive emulsion layer (R-2) Silver iodobromide emulsion (Em-1) 0.4〃 (Em-2) 0.3 Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 3.2 × 10 ^-4 (〃) 〃 (S-3) 0.2 × 10 ^{− 4} (〃) Cyan coupler (C-1) 0.50〃 (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006〃 (D-2) 0.01 High boiling solvent (OiL-1) 0.55 gelatin 1.0 fourth layer; high-sensitivity red-sensitive emulsion layer (RH) silver iodobromide emulsion (Em-3) 0.9 sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 1.6 × 10 ^-4 (〃) 〃 (S-3) 0.1 × 10 ^-4 (〃) Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D- 2) 0.02 High boiling solvent (OiL-1) 0.25 Gelatin 1.0 Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 Sixth layer; Low sensitivity green-sensitive emulsion layer (G-1) Silver iodobromide emulsion (Em- 1) 0.6〃 (Em-2) 0.2 Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-5) 0.8 × 10 ^-4 (（) Magenta coupler (M-1) 0.3) Colored magenta coupler (CM-1) 0.09 DIR compound (D-3) 0.025 〃 (D-4) 0.015 High boiling point solvent (OiL-4) 0.4 Gelatin 1.0 7th layer; Low sensitivity green-sensitive emulsion layer (G- H) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) 〃 (S-7) 2.0 × 10 ^-4 (（) 〃 (S -8) 0.3 × 10 ^-4 (〃 Magenta coupler (M-1) 0.11 Colored magenta coupler (CM-1) 0.07 DIR compound (D-4) 0.01 High boiling solvent (OiL-4) 0.17 Gelatin 1.0 Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (SC-1) 0.12 High boiling solvent (OiL-2) 0.15 Gelatin 1.0 Ninth layer; Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.255 (Em-2) ) 0.25 Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.600 (Y-2) 0.32 DIR compound (D-1) 0.003〃 (D-2) ) 0.006 high-boiling solvent (OiL-2) 0.18 gelatin 1.3 10th layer: low sensitivity blue-sensitive emulsion layer (B-H) silver iodobromide (Em-4) 0.5 sensitizing dye (S-10) 3.0 × 10 - ⁴ (mol / silver 1 mol) 〃 (S-11) 1.2 × 10 ^-4 (〃) Yellow coupler (Y-1) 0.18 〃 (Y-2) 0.10 High boiling point melting (O iL-2) 0.05 gelatin 1.0 11th layer; 1st protective layer (PRO-1) Silver iodobromide (Em-5) 0.3 UV absorber solid at room temperature (UV-1) 0.07UV (UV-2) 0.1 High boiling point melting (OiL-1) 0.07〃 (OiL-3) 0.07 Gelatin 0.8 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Sliding agent (MAX-1) 0.04 Gelatin 0.5 In addition to the above composition, each layer contains a surfactant SU-1
Hardener H-1 was added as needed.

The emulsions used in the above samples are as follows. Each is a monodisperse emulsion.

Em-1: average AgI content 7.5 mol% octahedron particle size 0.55 μm Em-2: average AgI content 4.0 mol% octahedron particle size 0.36 μm Em-3: average AgI content 8.0 mol% octahedron particle 0.84 μm Em-4: average AgI content 8.5 mol% Octahedral particle size 1.02 μm Em-5: average AgI content 2.0 mol% particle size 0.08 μm Em-6: average AgI content 9.0 mol% octahedral outer phase AgI content Em-7: average AgI content 4.0 mol% 14-sided outer phase AgI content 1.0 mol% Particle size 0.32 μm Em-8: average AgI content 9.0 mol% octahedral outer phase AgI content Emulsion having a ratio of 1.0 mol% and a particle size of 1.1 μm Em-6 to 8 was prepared according to the method described in JP-A-60-138538.

Sample No. 1 was changed by changing the emulsion grains in the ninth and tenth layers and the ultraviolet absorber in the first and eleventh layers as shown in Table 1.
o.2 to 7 were created. In Samples No. 2 and Nos. 4 to 7, no high-boiling solvents other than the ultraviolet absorber were used in the first and eleventh layers.

As No. 8, the amount of gelatin in the twelfth layer of No. 1 was 1.5 g / m
Samples increased to ² were also made.

Samples Nos. 1 to 8 prepared in this manner were prepared in three parts each, and used for evaluation of pressure resistance, sharpness, and sweating properties.

(Evaluation method) Pressure resistance An unexposed sample is scratched with a constant load of 5,10 g at a speed of 600 m / min using a sapphire needle (0.025 mmφ) of JIS K6718 standard. Processing,
After drying, the transmission density of the wound was measured. The density at this time was defined as pressure fog. That is, the lower the concentration, the better the pressure resistance. Table 2 shows the measurement results of Samples 1 to 8.

Sharpness White exposure was performed using a sharpness evaluation filter, and after the following development processing, the MTF (Modulation Trasfer Functi
on). Table 2 shows the relative values of the MTF at 20 lines / mm and 60 lines / mm. However, the MTF value of No. 1 was set to 100.

Sweating property For the evaluation of the sweating property, prepared Sample Nos. 1 to 8 were conditioned at 55% RH, sealed, heat-treated at 70 ° C. for 2 days, and then subjected to color development processing according to the following processing steps. .

 Table 2 shows the evaluation results of each sample after the treatment.

Processing time (38cc) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds The processing solution composition used in each processing step is as follows: It is.

Color developer composition 4-Amino-3-methyl-Nethyl-N- (β-hydroxyethyl) -aniline sulfate 4.8 g Sodium sulfite anhydrous 0.14 g Hydroxyamine 1/2 sulfate 1.98 g Sulfuric acid 0.74 g Anhydrous potassium carbonate 28.35 g Anhydrous potassium hydrogen carbonate 3.46 g Anhydrous potassium sulfite 5.10 g Potassium bromide 1.16 g Sodium chloride 0.14 g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20 g Potassium hydroxide 1.48 g Add water to make 1.

Bleaching solution composition Ethylene diaminetetraacetic acid iron ammonium salt 100.0
g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 and adjust the pH to 6.0 using aqueous ammonia.

Fixer composition Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.6 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH 6.0 with acetic acid.

Stabilizing solution composition Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

Evaluation of sweating: ×: The sample looks turbid when exposed to light. △: 〃 A little 〃 ○: No abnormality is found on the surface or inside.

Regarding the evaluation of the pressure resistance, ×: There is a problem in practical use Δ: There is a problem in practical use, but practically possible ○: No problem in practical use ◎: Excellent, no problem.

As is evident from Table 2, in the sample of the present invention, good results were obtained in all of the pressure resistance, sharpness, and perspiration. It is also apparent from Table 2 that the combination of the specific silver halide grains of the present invention and a UV absorber which is liquid at ordinary temperature can produce a remarkable synergistic effect on sharpness and pressure resistance.

〔The invention's effect〕

According to the present invention, a silver halide photographic light-sensitive material having excellent image quality in both sharpness and pressure fog can be provided. The effect of the present invention is a synergistic effect (in terms of sharpness and pressure fog) obtained by including the specific silver halide grains in combination with a specific ultraviolet absorber.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/815 G03C 1/035

Claims (1)

(57) [Claims] 1. A silver halide photographic material having a photographic component layer comprising at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide photographic material is contained in at least one of the photosensitive silver halide emulsion layers. Silver halide grains having an average silver iodide content higher than the silver iodide content of the outermost surface phase,
A silver halide photographic light-sensitive material characterized in that at least one of the photographic constituent layers contains at least one ultraviolet absorber which is liquid at normal temperature.