JPH0685057B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more specifically, stability during development processing (hereinafter referred to as processing stability) and thermal stability of raw film. The present invention relates to a silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material) having improved heat resistance (hereinafter referred to as heat resistance).

[Background of the Invention] In recent years, there has been a demand for the development of high-quality and homogeneous photosensitive materials, and at the same time, development processing has become more automated.
And has been speeded up. That is, even if a light-sensitive material having high image quality performance is not sufficiently stable at the time of development processing, not only the original performance of the light-sensitive material cannot be brought out but also a slight development It becomes a photosensitive material with a large variation in performance due to changes in processing conditions, and cannot meet the needs of users.

As a method for improving the processing stability, for example, a method of controlling the developability of silver halide, a method of using a coupler having a good developability, a method of improving with various additives, etc. are known. It is also known to improve processing stability by adding non-photosensitive fine grain silver halide to a hydrophilic hydrophilic colloid layer. For example, US Patent No.
3,523,022, 3,591,382, 3,737,317, JP-A-5
There are 0-23228 and 50-55332.

Although the effect of improving the processing stability by this method is remarkable,
It has the drawback of deteriorating the heat resistance of the silver halide emulsion layer adjacent to the non-photosensitive hydrophilic colloid layer to which fine grain silver halide is added, and is not sufficiently satisfactory.

[Object of the Invention] An object of the present invention is to provide a light-sensitive material in which the processing stability and the heat resistance of the raw film are simultaneously improved.

[Structure of the Invention] As a result of examining various materials based on the above technical background, the present inventor found that at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid were formed on a support. In each of the silver halide photographic light-sensitive materials having layers, at least one of the non-photosensitive hydrophilic colloid layers adjacent to the silver halide emulsion layer is a liquid benzotriazole compound at room temperature 1 mg / m ² to 1 g / m ² It has been found that the object of the present application can be achieved by incorporating a non-photosensitive fine grain silver halide.

Many benzotriazole compounds have been known as ultraviolet absorbers, and in particular, Tinuvin PS, 320, 326, 328 and the like manufactured by Ciba-Geigy are representative compounds.

However, due to the non-photosensitive fine grain silver halide in which the benzotriazole compound which is liquid at room temperature is added to the non-photosensitive hydrophilic colloid layer adjacent to the silver halide emulsion layer, deterioration of thermal stability is significantly prevented. What to do was a totally unexpected discovery.

[Detailed Description of the Invention] The preferred benzotriazole-based compound that is liquid at room temperature (hereinafter referred to as the compound of the present invention) used in the present invention is 2- (2'-hydroxyphenyl) benzotriazole-based compound that is liquid at room temperature. A compound of the following general formula [I]
Indicated by.

General formula [I] The benzotriazole compound used in the present invention is
More preferably, the 3'-position and the 5'-position of such 2- (2'-hydroxyphenyl) benzotriazole,
And, if necessary, it has a substituent at the 5-position.

As such a substituent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or the like is bonded to the 3'-position and the 5'-position.

Further, a substituent such as a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group is bonded to the 5-position.

In this case, it is necessary to be liquid at room temperature in order to obtain the effects of the present invention, and it is preferable that the liquid is liquid at 15 ° C.

Next, 2 represented by the above general formula [I] which is a liquid at 15 ° C.
Representative specific examples of the-(2'-hydroxyphenyl) benzotriazole compound are shown below, but the present invention is not limited to these.

Synthetic examples of these compounds can be synthesized according to the methods described in JP-B-42-26187 and JP-A-57-142975.

The benzotriazole-based compound that is liquid at room temperature of the present invention is
It may be added alone in any non-photosensitive hydrophilic colloid layer containing a non-photosensitive fine grain silver halide described below, or in a non-photosensitive hydrophilic colloid layer adjacent to the colloid layer, or You may add together 2 or more types.

Further, the liquid benzotriazole-based compound of the present invention,
Any ultraviolet absorber can be added in combination.
UV absorbers that can be used in combination are solid at room temperature. 2
-(2'-Hydroxyphenyl) benzotriazole type UV absorbers, for example, US Pat. Nos. 2,882,150 and
2,739,971, No. 2,709,067, No. 2,875,053, No. 3,352,681, No. 2,739,888, No. 2,719,162,
Thiazolidones as described in Nos. 2,808,330 and 3,365,295, JP-A-57-10537, and JP-B-48-304.
No. 92, No. 49-43888, No. 48-31255, No. 48-35376, acrylonitriles as described in Belgian Patent No. 833,511, British Patent No. 1,321,355, U.S. Patent No. 3,2.
Benzophenones as described in 15,530, as well as U.S. Patents 3,271,156, 2,748,021 and 2,68.
It is also possible to use an ultraviolet absorber as described in 5,512, 2,763,566, 2,632,701 and West German Patent 1,023,859.

The amount of the compound of the present invention to be added to the non-light-sensitive hydrophilic colloid layer is preferably from ^{1mg / m 2 ~1g / m 2} , still more preferably from ^{5mg / m 2 ~600mg / m 2} .

To incorporate the compound of the present invention into the non-photosensitive hydrophilic colloid layer, the compound of the present invention is mixed alone or with other additives, and a low-boiling solvent and / or a high-boiling solvent is added if necessary. , An aqueous solution containing a hydrophilic colloid such as a surfactant and gelatin, and emulsified and dispersed by a high-speed rotating mixer, a colloid mill, an ultrasonic dispersion device, etc., and the obtained dispersion liquid is a non-photosensitive material having a hydrophilic colloid substance. It may be added to the coating solution for the hydrophilic colloid layer and coated on the support or on the emulsion layer or the like coated on the support.

As the non-photosensitive fine grain silver halide according to the present invention, any non-photosensitive one can be used as long as it is substantially non-photosensitive, that is, one which is not substantially developed in the developing solution. It is preferable that it is not substantially developed and dissolved. The average particle size is preferably 0.3 μm or less, and more preferably 0.02 to 0.2 μm. The distribution of particles may be wide or narrow, but a narrow distribution is preferable.

The silver halide grains used as the substantially non-photosensitive silver halide fine grains include any of silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like. These silver halides may be used alone or in combination of two or more. Further, the silver halide grains are preferably silver halide containing silver bromide from the viewpoint of solubility, and particularly 10 mol%
Silver iodobromide containing less silver iodide is preferred. The silver halide grains may be physically aged with a rhodanate ion, a cyano ion, a thiocyanate ion or the like, or may be etched with a silver halide solvent. These silver halide grains are manufactured by various manufacturing methods such as a neutral half-ammonia method and ammoniu method, and also manufactured by various manufacturing types such as a simultaneous mixing method and a conversion method.

The non-photosensitive fine grain silver halide of the present invention may be added to any non-photosensitive hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably the farthest silver halide emulsion from the support. It is preferable to add it to the non-photosensitive hydrophilic colloid layer adjacent to the layer on the side far from the support.

The non-photosensitive fine grain silver halide used in the hydrophilic colloid layer is generally applied at 0.01 to 1 gAg / m ² , but preferably applied at 0.1 to 0.5 gAg / m ^2. To be The non-photosensitive layer includes a matting agent such as colloidal silica and polymethylmethacrylate, a high boiling point solvent (eg, tricresyl phosphate, dioctyl phthalate), an antioxidant, a lipophilic component such as a hydroquinoline derivative, and a surfactant. The coating aid, the gelatin hardened milk and the like may be used at the same time.

Gelatin is generally used as a binder for the non-photosensitive hydrophilic colloid layer, but colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed instead of part or all of gelatin. Cellulose derivatives such as cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose and methyl cellulose, and synthetic binders may be used.

In the light-sensitive material of the present invention, other known couplers can be used together with the benzotriazole compound and the non-photosensitive fine grain silver halide which are liquid at room temperature. Such couplers include magenta couplers, yellow couplers and cyan couplers. Specific examples of magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based couplers. Such magenta couplers include U.S. Pat.Nos. 2,600,788 and 2,9
83,608, 3,062,653, 3,127,269, 3,
No. 311,476, No. 3,419,391, No. 3,519,429, No. 3
No. 3,558,319, No. 3,582,322, No. 3,615,506, No. 3,834,908, No. 3,891,455, West German Patent 1,810,464
Issue, West German patent application (OLS) 2,408,665, 2,417,945
No. 2, No. 2,418,969, No. 2,424,467, and Japanese Patent Publication No. 40-6031
No. 4, JP-A-49-74027, 49-74028, 49-129538
50, 50-60233, 50-159336, 51-20826, 5
1-26541, 52-42121, 52-58922, 53-55122
And Japanese Patent Application No. 55-110943.
Among such magenta couplers, as a colored magenta coupler, an arylazo-substituted or heteroarylazo-substituted compound is used at the active site of the colorless magenta coupler, and, for example, U.S. Pat.
No. 2, No. 2,688,539, No. 2,725,292, No. 2,983,60
No. 8, No. 3,005,712, No. 3,519,429, British Patent No. 8
The compounds described in 00,262, 1,044,778, Belgian Patent No. 676,691 and the like can be mentioned. Examples of the yellow coupler include benzoylacetanilide type and pivaloylacetanilide type yellow couplers, and 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction. .

Specific examples of yellow couplers that can be used in the present invention are described in US Pat.
No. 2,875,057, No. 3,265,506, No. 3,408,194, No. 3,551,155, No. 3,582,322, No. 3,725,072,
No. 3,891,445, West German patent 1,547,868, West German application published
2,219,917, 2,261,361, 2,414,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133.
No. 48-73147, No. 50-6341, No. 50-87650, No. 50-
123342, 50-130442, 51-21827, 51-102636
No. 52-82424, No. 52-115219, No. 58-95346, etc.

Further, the cyan coupler includes a phenol or naphthol derivative, and the colored cyan coupler further includes a compound in which an arylazo-substituted phenoxy group is substituted at the coupling position of a colorless cyan coupler through an alkoxy group. Can be mentioned.

Such cyan couplers include, for example, US Pat.
No. 2,423,730, No. 2,474,293, No. 2,801,171, No. 2,895,826, No. 3,476,563, No. 3,737,326,
No. 3,758,308, No. 3,893,044, JP-A-47-3
No. 7425, No. 50-10135, No. 50-25228, No. 50-112038
Nos. 50-117422 and 50-130441, and couplers described in JP-A-58-98731 are preferable. Further, as a colored cyan coupler as a masking coupler, for example, US Pat.
1,908, 3,034,892, British patent 1,255,111,
Examples thereof include compounds described in JP-A-48-22028.

Further, U.S. Pat.No. 3,476,563, JP-A-50-10135, 50-
Colored cyan couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidation product of the color developing agent as described in 123341 can also be used.

Conventionally known magenta couplers, yellow couplers and cyan couplers used in the present invention, when incorporated in a photosensitive layer together with a diffusible and diffusion resistant DIR compound, are 0.002 mol to 0.5 mol per mol of silver halide, It is preferably used in the range of 0.009 to 0.35 mol.

The light-sensitive material of the present invention comprises a phenylureido group at the 2-position together with a diffusible and diffusion-resistant DIR compound or its precursor
A naphthyl ureido group or a heterocyclic ureido group can be used in combination with an ureido type phenolic cyan coupler having an acylamino group at the 5-position. Such an ureido-type phenol-type cyan coupler is disclosed in Japanese Patent Application No. 56-65134.
57-204543, 57-204544, 57-204545. When the ureido phenolic cyan coupler is used in combination with the diffusive and diffusion resistant DIR compound, the added layer may be the same as or different from the layer containing the diffusible and diffusion resistant DIR compound. It doesn't matter. When the ureido type cyan coupler is used in combination with the diffusible and antidiffusive DIR compound, the color recovery failure of the cyan dye, which tends to occur when the bleaching ability during the bleaching process is lowered, is improved, and the dye has a good color balance. Images can be obtained.

Furthermore, in the present invention, in order to improve the graininess of the dye image, the dye that is formed is slightly mobile when it undergoes a coupling reaction with an oxidant of a color developing agent together with a diffusible and diffusion resistant DIR compound. Can be used. Such couplers are described in, for example, JP-A-57-82837, JP-A-58-217932, and Japanese Patent Application No. 58-174755, and are resistant to diffusion in an emulsion.
The coupler can be added in the same layer as the layer in which the diffusible and diffusion resistant DIR compound is added or in a different layer, but a plurality of halogens having different sensitivities having substantially the same color sensitivity. Of the silver halide emulsion layers, preferably
It is contained in the high-sensitivity layer. The addition amount of this coupler is 0.00
1~0.5g / m ^2, preferably from 0.005 to 0.5 / m ^2.

As the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide emulsion used in the art can be applied. For example, it may contain silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide crystals, or a mixture of these crystals. The silver halide emulsion may be large grains or small grains and may be monodisperse or polydisperse. The silver halide crystal may be any of cubic crystal, octahedron, epitaxial mixed crystal and the like. The emulsion can be a negative emulsion or a direct positive emulsion. They are mainly a surface latent image type emulsion that forms a latent image on the surface of a silver halide grain, an internal latent image type emulsion that forms a latent image inside a silver halide grain, or a surface latent image type emulsion and an internal latent image. Mixtures with mold emulsions can be used.

The silver halide emulsion can be prepared by various methods such as a commonly used method, for example, the method described in Japanese Patent Publication No. 46-7772, that is, a silver salt having a solubility higher than that of silver bromide. A so-called conversion emulsion is prepared by forming an emulsion of salt grains and then converting at least a part of the grains into a silver bromide or silver iodide salt, or a fine grain halogen having an average grain size of 0.1 μm or less. It can be prepared by a foaming method such as a method for producing a Lippmann emulsion made of silver halide.

When the silver halide used in the present invention is required to be a high-sensitivity silver halide emulsion in absolute value, the silver halide is silver iodobromide containing 1 to 10 mol% of silver iodide. And the particle size is preferably 0.5 to 3.0 μm. Further, the silver halide used as a low-sensitivity silver halide emulsion in combination with the above-mentioned high-sensitivity emulsion is preferably silver iodobromide containing 1 to 12 mol% of silver iodide and has a grain size of 0.1 to 0.8 μm. Preferably there is.

As the binder of the silver halide emulsion layer, conventionally known binders are used, such as gelatin, derivative gelatin,
Synthesis of homopolymers such as grant polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole, polyacrylamide, etc. Any one such as a hydrophilic polymer is included.

The silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder solution can be sensitized with a chemical sensitizer. The chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types, that is, a noble metal sensitizer, a sulfur sensitizer, a selenium sensitizer and a reduction sensitizer.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium and platinum can be used.

When a gold compound is used, ammonium thiocyanate and sodium thiocyanate can be used together.

As the sulfur sensitizer, in addition to active gelatin, a sulfur compound can be used.

As the selenium sensitizer, active and inactive selenium compounds can be used.

Reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

The emulsion used in the present invention contains 5 × 10 ^{−3 to} 3 × 10 ⁻³ mol of an appropriate sensitizing dye for 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as the sensitizing dye used for the green light-sensitive emulsion, for example, U.S. Patent Nos. 1,939,201, 2,072,908, and 3,73
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in 9,149, 2,945,763, and British Patent No. 505,979. Further, as the sensitizing dye used for the red light-sensitive emulsion, for example, U.S. Patent Nos. 2,269,234 and 2,270,3.
No. 78, No. 2,442,710, No. 2,454,629, No. 2,776,
Typical examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes described in No. 280 and the like. Furthermore, U.S. Pat.
No. 995, No. 2,493,748, No. 2,519.001, West German patent 9
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in No. 29,080 can be advantageously used in a green light sensitive emulsion or a red light sensitive emulsion.

These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example is
U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,
No. 060, No. 3,522,052, No. 3,527,641, No. 3,61
No. 7,293, No. 3,628,964, No. 3,666,480, No. 3,6
72,898, 3,679.428, 3,703,377, 3,
No. 769,301, No. 3,814,609, No. 3,837,862, No. 3
4,026,707, British Patents 1,344,281, 1,507,803
No. 4, Japanese Patent Publication No. 43-4936, No. 53-12375, JP-A-52-109925
No. 52-110618.

As the silver halide used in the red-sensitive silver halide emulsion layer of the present invention, those having a silver iodide content of 2% to 15 mol% are preferable, and particularly, salt odor having a silver iodide content of 4% to 10 mol%. Silver halide is preferred.

The light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in British Patent No.
584,609, 1,177,429, JP-A-48-85130, 49
-99620, 49-114420, 52-108115, U.S. Patent No.
No. 2,274,782, No. 2,533,472, No. 2,956,879, No. 3,148,187, No. 3,177,078, No. 3,247,127,
No. 3,540,887, No. 3,575,704, No. 3,653,905
No. 3, No. 3,718,472, No. 4,070,352, No. 4,071,31
It is described in No. 2.

The photographic material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure Magazine 17643. , Plasticizers, wetting agents and the like can be used.

As the support of the light-sensitive material used in the present invention, for example, a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film and the like are preferable, but also baryta paper, polyethylene Coated paper, polypropylene synthetic paper,
It is also possible to use a support in which a reflective layer is provided side by side or a reflector is used in combination. These supports are appropriately selected depending on the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layers and other constituent layers used in the present invention. Also, U.S. Pat.Nos. 2,761,791 and 2,941,
It is also possible to use simultaneous coating of two or more layers by the method described in 1,898.

Further, in the light-sensitive material used in the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose in addition to the non-light-sensitive hydrophilic colloid layer.
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers. In these constituent layers, a hydrophilic colloid which can be used in the emulsion as described above can be similarly used as a binder, and various kinds thereof can be contained in the emulsion layer as described above. The above photographic additives can be incorporated in the same manner.

The light-sensitive material of the present invention includes all kinds of color photographic light-sensitive materials such as a color negative film, a color positive film, a color reversal film and a color paper, and is particularly useful in a color negative film.

As the color developing agent contained in the color developing solution for processing the light-sensitive material of the present invention, aromatic primary amine compounds, particularly p-phenylenediamine compounds are preferable, and N, N-diethyl-p-phenylenediamine is preferable. Hydrochloride, N-ethyl-
p-phenylenediamine hydrochloride, N, N-dimethyl-p-
Phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-
N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N- (2
-Methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate, N, N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N- (β-hydroxyethyl) -3-methyl -4-Aminoaniline and the like can be mentioned. These color developing agents may be used alone or in combination of two or more kinds.

In addition, LFA Nason (El F Nason) "Photographic Processing Chemistry" (Photographic Processing Chemistry) (Focal
Prese, 1966) (Focal Press, 1966) 2
26-229, U.S. Pat.Nos. 2,193,013 and 2,592,364
Nos. 48-64933, and the like.

The light-sensitive material used in the present invention can contain these color developing agents in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof. The color developing agent precursor is alkaline,
It is a compound capable of forming a color developing agent, and examples thereof include a Schiff base precursor with an aromatic aldehyde compound, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a urethane type precursor. The breakers of these aromatic primary amine type color developing agents are disclosed in U.S. Pat. Nos. 2,507,114, 2,695,234 and 3,
342,599, 3,719,492, British Patent 803,783,
It is described in JP-A-53-185628, JP-A-54-79035, and Research Disclosure Magazines 12146, 13924, and 15159. The addition amount of these aromatic primary amine color developing agents or their precursors is generally in the range of 0.1 to 5 mol, preferably 0.3 to 3 mol, per mol of the photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. To incorporate these color developing agents or precursors in the light-sensitive material, water, methanol, ethanol,
It can also be added by dissolving in a suitable solvent such as acetone,
It can also be added as an emulsion dispersion using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc., and is added by impregnating a latex polymer as described in Research Disclosure Magazine 14850. You can also

The color developing solution of the present invention is, for example, an alkali agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, and tribasic sodium phosphate, and a development inhibitor such as sodium bromide and potassium bromide. , Various organic solvents such as methanol, ethanol, acetone, butanol, benzyl alcohol, phenoxybutanol, diethylene glycol, ethylene glycol, N, N-dimethylformamide, hydroxylamine, preservatives such as sodium sulfite, citrazinic acid, polyethylene glycol, Development modifiers such as polyvinylpyrrolidone, water-soluble optical brighteners such as diaminostilbene compounds, heavy metal ion concealing agents such as ethylenediaminetetraacetic acid and alkyliminodiacetic acid, development accelerators and other various known additives are required. May be included accordingly That.

The pH value of this color developing solution is usually 7 or higher, most commonly from about 9.5 to about 12. The higher the pH, the faster the developing speed and the shorter the time required for the color developing step, but the stability of the processing solution is deteriorated, and it is generally not preferable to set the pH to 11 or more.

Regarding the temperature, the higher the temperature, the shorter the processing time of the color developing step, but if the processing temperature is too high, problems such as increased fog and decreased stability of the processing liquid will generally occur.
It is not preferable to set it to 40 degrees or more.

The processing time in the color developing step of the present invention is from 45 seconds to 5 seconds.
Minutes, preferably between 60 seconds and 4 minutes.

The light-sensitive material of the present invention has the effects of not causing defective recolorability even when subjected to the one-bath bleach-fixing treatment for the purpose of rapid processing, and improving graininess and good visual color reproducibility. The obtained light-sensitive material of the present invention is preferably subjected to a one-bath bleach-fixing process.

The light-sensitive material of the present invention may be processed separately from the bleaching step-fixing step.

Further, other photographic processing steps other than the bleach-fixing processing step of the present invention may be carried out in the same manner as ordinary processing steps.

As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, ferricyanide, dichromate, organic complex salts of iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or quinic acid. Complex salts of organic acids such as acids, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used.

As the bleaching agent in the bleach-fixing process of the present invention, metal complex salts of organic acids are particularly preferable among the above.

The metal complex salt of an organic acid has an action of oxidizing metal silver produced by development to convert it to silver halide, and its structure is an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid, and iron, cobalt, The metal ions such as copper are coordinated. The most preferred organic acid used for forming such a metal complex salt of an organic acid is, for example, aminopolycarboxylic acid.

These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The following may be mentioned as typical examples of the aminopolycarboxylic acid.

Ethylenediaminetetraacetic acid ethylenediamine-N- (β-hydroxyethyl) -N,
N, N'-Triacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Cyclohexanediaminetetraacetic acid Iminodiacetic acid Methyliminodiacetic acid Ethyliminodiacetic acid Hydroxyethyliminodiacetic acid Propyliminodiacetic acid Butyliminodiacetic acid Dihydroxyethylglycine Ethyletherdiaminetetraacetic acid Glycoletherdiaminetetraacetic acid Ethylenediaminetetrapropione Acid phenylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N- (β-hydroxyethyl) -N,
N, N'-triacetic acid sodium salt Propylenediaminetetraacetic acid sodium salt Nitrilotriacetic acid sodium salt Cyclohexanediaminetetraacetic acid sodium salt The metal in the metal complex salt of an organic acid used in the present invention is a metal capable of coordinatively bonding with an organic acid. , For example, chromium, manganese, iron, cobalt, nickel, copper, etc.,
Particularly preferred for the present invention is iron.

The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned organic acid and metal, and particularly preferable are ferric salts of ethylenediaminetetraacetic acid, for example, iron (II) sodium ethylenediaminetetraacetate and ethylenediaminetetraacetic acid. It is iron (II) acetate ammonium. Further, metal complex salts of two or more kinds of organic acids having different structures may be used in combination. The specific amount used is about 5 to 400 per processing liquid.
It is preferable to use g, especially about 10 to 200 g per processing solution.

The bleach-fixing solution used in the present invention contains, as a bleaching agent, a metal complex salt of an organic acid as described above (for example, an iron complex salt), and a silver halide fixing agent such as thiosulfates, thiocyanates and thioureas. A liquid having a composition containing is applied. Further, from a bleach-fixing solution comprising a composition containing a small amount of a halogen compound such as potassium bromide in addition to a bleaching agent and the above-mentioned silver halide fixing agent, or conversely, comprising a composition containing a large amount of a halogen compound such as potassium bromide. It is also possible to use a bleach-fixing solution containing a bleach-fixing solution, and a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide.

[Examples] Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 A sample 1 was prepared by applying the material on a support made of a cellulose triacetate film subjected to an undercoating process as shown below.

First layer: Green-sensitive low-sensitivity silver halide emulsion layer (GL layer) Silver iodobromide emulsion containing 6 mol% of silver iodide (average grain size
0.5 μm) were chemically sensitized by adding gold and sulfur sensitizers, and further a green light-sensitive sensitizing dye was added (0.5 mol of silver halide and 40 g of gelatin per 1 kg of this emulsion). Next, 380 ml of the following dispersion (M-1) was added to 500 g of this emulsion to prepare a green-sensitive low-sensitivity silver halide emulsion.
It was applied at 5 g / m ² .

Second layer: Green sensitive high-sensitivity silver halide emulsion layer (GH layer) Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.7 μm) was chemically sensitized in the same manner as in the above emulsion (0.5 mol of silver halide and gelatin per 1 kg of this emulsion).
Including 40g). Then, the following dispersion (M
-2) 110 ml was added to prepare a green-sensitive high-sensitivity silver halide emulsion, which was coated so that the silver coating amount would be 1.3 g / m ² .

Third layer: intermediate layer A solution prepared by adding water to 30 g of gelatin was applied so that the amount of gelatin applied would be 0.8 g / m ² .

Fourth layer: yellow filter layer A gelatin solution containing 30 g of gelatin, yellow colloidal silver, 2,5-di-tert-octylhydroquinone and a hardener was applied so that the amount of gelatin would be 0.8 g / m ² .

Dispersion (M-1) 40 g of the following coupler and 8 g of the coupler were dissolved in a mixture of 48 g of tricresyl phosphate (TCP) and 145 g of ethyl acetate (EA), and 4.5 g of sodium triisopropylnaphthalenesulfonate (SUR-1) was added. The mixture was added to 400 ml of a 10% gelatin aqueous solution contained and emulsified and dispersed in a colloid mill to prepare 1000 ml.

Dispersion (M-2) A dispersion (M-2) having the following composition was prepared in the same manner as the dispersion (M-1).
-2) was prepared.

Coupler 30 g Coupler 9 g TCP 78 g EA 120 g 10% Gel 390 g SUR-1 4.4 g Preparation amount 1000 ml Sample 1A was prepared in this manner. The fine grain silver halide and the dispersions (U-1) to (U-3) were added to prepare sample No. 1B and sample Nos. 2 to 7.

Fine grain silver halide A silver iodobromide emulsion containing 3 mol% of silver iodide and having an average grain size of 0.06 μm was prepared by a conventional method.

Dispersion (U-1) The following compounds and 10 g of each were dissolved in a mixture of 16 g of dioctyl phthalate (DOP) and 100 g of ethyl acetate (EA) and containing 2.7 g of sodium triisopropylnaphthalene sulfonate (SUR-1) 10 % Gelatin aqueous solution 480 ml
In addition, the mixture was emulsified and dispersed by a colloid mill to prepare 1000 ml.

Dispersion (U-2) Instead of the compound in the dispersion (U-1) and
A dispersion was prepared in the same manner as the dispersion (U-1) except that 20 g of the compound of the present invention UV-6L was used.

Dispersion (U-3) Dispersion (U-3) except that 20 g of compound UV-15L of the present invention was used in place of the compound in Dispersion (U-1).
It was dispersed and prepared in the same manner as in -1).

[Compounds used for preparing samples No. 1A and 1B to No. 7] Each of the samples thus obtained was allowed to stand at a temperature of 65 ° C. and a relative temperature of 20% for 3 days, and then subjected to green exposure through a wedge by a usual method, and then the following development treatment was carried out.
The results in the table were obtained.

The difference in fog value in Table 2 is a value obtained by subtracting the fog value of the high temperature untreated sample from the fog value of the sample after the high temperature treatment. The larger this value is, the poorer the thermal stability is.

In addition, for the sample not subjected to the high temperature treatment, the gamma value (γ _o ) under the following developing conditions and the gamma value (γ _a ) and the ratio γ _a / γ at the developing time (2 minutes 55 seconds) shorter than that by 20 seconds.
_o × 100 (%) was measured. The closer the ratio is to 100 (%), the better the development stability.

Development process (38 ℃) Processing time Color development 2 minutes 30 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Settling 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Used in each processing step The composition of the treated liquid is as follows.

Color developer composition 4-Amino-3-methyl-N-ethyl-N (β-hydroxyethyl) -aniline sulfate 4.8 g Anhydrous sodium sulfite 0.14 g Hydroxyamine 1/2 sulfate 1.98 g Sulfuric acid 0.74 g Anhydrous potassium carbonate 28.85g anhydrous potassium hydrogen carbonate 3.46g anhydrous potassium sulfite 5.10g potassium bromide 1.16g sodium chloride 0.14g nitrilotriacetic acid trisodium salt (monohydrate) 1.20g potassium hydroxide 1.48g Add water to make 1.

Bleaching liquid composition Ethylenediaminetetraacetic 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 adjust to pH 6.0 and adjust to pH 6.0.

Fixer composition Ammonium thiosulfate 17.5g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1 and adjust to pH 6.0 with acetic acid.

Composition of stabilizing solution Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

It is clear from Table 2 that Samples No. 3 to No. 6 according to the present invention have excellent heat resistance and processing stability.

Example-2 Sample-8 was prepared by sequentially coating the following layers from the support side on a support made of a cellulose triacetate film subjected to an undercoating process.

1st layer: Antihalation layer containing black colloidal silver (2.5 μm dry film thickness) 2nd layer: Intermediate layer made of gelatin (1.0 μm dry film thickness) 3rd layer: Red-sensitive low-sensitivity silver halide emulsion layer (RL Layer) Silver iodobromide emulsion containing 6 mol% of silver iodide (average grain size
0.5 μm, containing 0.25 mol of silver halide emulsion and 15 g of gelatin per 500 g of emulsion) were prepared by an ordinary method.
g was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'-di- (3-sulfopropyl) -4,5,4 ', 5'- as a red-sensitizing dye. Dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9-ethyl-
3.3'-Di- (3-sulfopropyl) thiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-3 ', 9-diethyl-3- (4-sulfobutyl) oxythiacarbocyanine hydroxide were added, followed by 4 -Hydroxy-6-
0.25 g of methyl-1,3,3a, 7-tetrazaindene was added.

Next, 420 ml of the following dispersion (C-1) was added to 500 g of this emulsion to prepare an emulsion, which was coated so as to have a dry film thickness of 3.0 μm.

Fourth layer: Red-sensitive high-sensitivity silver halide emulsion layer (RH layer) Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.6 μm, containing 0.25 mol of silver halide and 15 g of gelatin per 500 g of emulsion) were chemically sensitized in the same manner as in the above emulsion, and 185 ml of the following dispersion (C-1) was added to 500 g of this emulsion.
Was added to prepare an emulsion, and the emulsion was coated such that the silver coating amount was 1.5 g / m ² .

Fifth layer: Intermediate layer A solution prepared by dissolving 28 g of gelatin in water is added to give a gelatin coating amount of 0.8.
It was applied so as to be g / m ² .

Sixth layer: Green-sensitive low-sensitivity silver halide emulsion layer (GL layer) The same emulsion as the first layer of Example-1 was coated so as to have a silver coating amount of 1.5 g / m ² .

Seventh layer: Green-sensitive high-sensitivity silver halide emulsion layer (GH layer) The same emulsion as the second layer of Example-1 was coated so that the silver coating amount would be 1.3 g / m ² .

Eighth layer: intermediate layer A gelatin solution was applied so that the amount of gelatin applied would be 0.8 g / m ² .

Ninth layer: yellow filter layer A gelatin solution containing gelatin, yellow colloidal silver, and 2,5-di-tert-octylhydroquinone was applied so that the amount of gelatin would be 1.0 g / m ² .

Layer 10: Blue-sensitive low-sensitivity silver halide emulsion layer (BL layer) Silver iodobromide emulsion containing 6 mol% of silver iodide (average grain size
0.5 μm, 0.25 mol of silver halide per 500 g of emulsion and 40 g of gelatin are chemically sensitized, and 1350 ml of the following dispersion (Y-1) is added to 500 g of this emulsion to prepare a blue-sensitive low-sensitivity silver halide emulsion. Then, it was applied so that the amount of silver applied would be 0.5 g / m ² .

11th layer: Blue sensitive high-sensitivity silver halide emulsion layer (BH layer) Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.8 µm, 0.25 mol of silver halide per 500 g of emulsion and 40 g of gelatin are chemically sensitized, and 500 ml of the following dispersion (Y-1) is added to 500 g of this emulsion to prepare a blue-sensitive high-sensitivity silver halide emulsion. Then, it was applied so that the amount of silver applied would be 0.6 g / m ² .

12th layer: intermediate layer A gelatin solution containing 250 ml of the dispersion (U-1) per 28 g of gelatin was coated so that the amount of gelatin was 0.8 g / m ² .

Thirteenth layer: Protective layer A gelatin solution containing 24 g of gelatin, a matting agent (silica having an average particle size of 3 μm) and a hardening agent is applied at a gelatin loading of 0.6 g / m 2.
^It was applied so as to be ² .

Dispersion (C-1) Dispersion (C-1) was prepared in the same manner as dispersion (M-1).

Coupler 30 g Coupler 3.0 g TCP 33 g EA 198 g 10% Gel 440 ml SUR-1 2.0 g Preparation amount 1000 ml Dispersion (Y-1) Dispersion (Y-1) by the same operation as dispersion (M-1) Was prepared.

Coupler 50.0 g TCP 5.0 g EA 165 g 10% Gel 370 ml SUR-1 4.0 g Preparation amount 1000 ml Sample No. 8 was prepared in this manner. Further, as shown in Table 3 below, sample No. 9 to No. 1l was prepared.

[Compounds used to prepare samples No.8 to No.11] These samples were tested at 65 ° C and a relative temperature of 20% as in Example-1.
Was left for 3 days, white exposure was given through the wedge, and then the same development processing as described in Example-1 was performed. Further, with respect to the sample which was not subjected to the high temperature treatment, the treatment stability was evaluated by the same method as described in Example-1.
The results are shown in Table 4.

From Table 4, samples No. 9 to No. 11 of the present invention had good heat resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-50533 (JP, A) JP-A-59-68731 (JP, A) JP-A-47-1026 (JP, A) JP-B 42- 26187 (JP, B1)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on a support, which is adjacent to the silver halide emulsion layer. A silver halide photograph characterized in that at least one of the non-photosensitive hydrophilic colloid layers contains a liquid-state benzotriazole compound at 1 mg / m ² to 1 g / m ² and a non-photosensitive fine grain silver halide. Photosensitive material.