JPH0627562A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a photographic sensitive material having high sensitivity and low fog density and capable of rapid development. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on the base, the silver halide in at least one silver halide emulsion layer contains >=95mol% silver chloride and the silver halide emulsion has been subjected to reduction sensitization in the presence of a tetrazaindene compd. having no sulfur-contg. substituent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, which has high sensitivity and excellent storage stability.
The present invention relates to a silver halide photographic light-sensitive material having improved dye adsorption.

[0002]

2. Description of the Related Art In recent years, demands for improving rapid processing performance of color photographic paper have become stronger and stronger, and many studies have been made. It is well known that increasing the silver chloride content of the silver halide emulsion used results in a dramatic increase in development rate. The silver halide used in the silver halide photographic light-sensitive material is generally chemically sensitized in order to obtain desired sensitivity, gradation and the like. As the method, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a noble metal sensitization method using gold or other noble metal compounds, a reduction sensitization method using a reducing substance, etc., alone or in combination. The method used in is known. For these sensitization methods, see THJeme
s), The Theory of the Photographic Process, 4th Edition (Macmillan Co. 1977), pages 149-160 and 164-165.

However, when a silver halide emulsion having a high silver chloride content is subjected to reduction sensitization, addition of a small amount of reduction sensitizer causes a large fog and an emulsion having high sensitivity cannot be obtained. On the other hand, tetrazaindene compounds are known as stabilizers for photographic emulsions, antifoggants, and desensitizers. Specifically, Research Disclosure Magazine 307, 866
Page. Regarding the improvement of the storage stability of an emulsion sensitized by sulfur in the presence of a tetrazaindene compound, disclosed in JP-B-4-11011, and the stability of latent image of an emulsion subjected to reduction sensitization is disclosed in JP-A-3-123340. However, there is no knowledge about suppression of large fog that appears during reduction sensitization. Therefore, an emulsion which is reduction-sensitized to high sensitivity by suppressing the development of fogging is desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material having a small fog, a high sensitivity, an excellent storability and a rapid development processing. Furthermore, another object of the present invention is to provide a silver halide light-sensitive material having improved dye adsorption.

[0005]

Such an object is achieved by the present invention described below. (1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one silver halide emulsion layer is composed of 95 mol% or more of silver chloride. And a silver halide emulsion obtained by subjecting the silver halide emulsion to reduction sensitization in the presence of a tetrazaindene compound having no substituent containing sulfur. . (2) The silver halide photographic light-sensitive material as described in (1) above, wherein the silver halide emulsion is reduction-sensitized and then treated with a solid substance carrying metal ions. (3) The silver halide photographic light-sensitive material as described in (2) above, wherein the metal ion is a metal ion having an atomic number of 21 or more. (4) The solid material carrying the metal ions is an ion exchange resin or a chelate resin,
(2) The silver halide photographic light-sensitive material described above.

The present invention will be described in detail below. The silver halide of the present invention is a high chloride silver halide composed of 95 mol% or more of silver chloride, more preferably pure silver chloride. The emulsion grains of the present invention may have a uniform crystal structure inside or may have different halogen compositions inside and outside, and silver halides having different compositions may be joined by epitaxial joining. . The silver bromide-rich layer on the surface and in the vicinity of it is formed by the so-called conversion method.
It may be formed by converting bromide ion to chloride ion. The average grain size of the silver halide of the present invention is not particularly limited, but is 0.1 μm to 5 μm, preferably
It is 1.5 μm or less. The grain size distribution of the silver halide of the present invention may be polydisperse or monodisperse, but monodisperse is preferable. The emulsion of the present invention may contain silver halide of any crystal habit. Emulsions containing cubic grains rather than spherical, tabular grains and octahedral grains are preferred for the present invention.

With silver halide grains having a high silver chloride content, generally only cubic grains having a (100) plane can be obtained, but if devised, octahedral grains having a (111) plane can be obtained. Known in the literature. Specifically, Claes et al .; The Journal Photographic Science, 21.
Vol. 39 (1973) and Vyrach; International Cong.
ress of Photographic Science, pp. 13, 122 (19
78). The former uses compounds such as adenine and dimethylthiourea. From the viewpoint of the structure of the compound, the compound such as adenine may be a compound strongly adsorbed to silver halide, or may be a compound having unstable sulfur molecules and easily causing fog.

The latter has octahedral silver chloride grains using ammonia and a large amount of cadmium nitrate, but cadmium has many problems in practical use in terms of pollution. The use of ammonia is not preferable because high-silver chloride grains are apt to cause fog, and it is preferable that a silver chloride octahedron can be prepared without using ammonia. Temperature during particle formation is 10 ° C
-95 degreeC, Preferably it is 40-90 degreeC. The pH at the time of particle formation is not particularly limited, but a neutral to acidic range is preferable. Further, a silver halide solvent may be used at the time of production.

The reduction sensitization referred to in the present invention is a method of adding a known reduction sensitizer to the silver halide emulsion after grain formation. Known reduction sensitizers include stannous salts, amines and polyamines, hydrazine derivatives, formamidisulfinic acid, silane compounds and borane compounds. Ascoscorbic acid or its derivative is also useful as a reduction sensitizer. In the present invention, these compounds can be selected and used, or two or more kinds of compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid or its derivative is preferable. Thiourea dioxide and dimethylamine borane are particularly preferable.

The tetrazaindene compound used in the present invention is known as a stabilizer for photographic emulsions and an antifoggant, and is described in the above-mentioned Research Disclosure, Vol. 307, page 866. It is considered that this adsorbs on silver halide and limits the reaction site to suppress the formation of fog nuclei by the reduction sensitizer. The tetrazaindene compound used in the present invention is preferably a tetrazaindene compound having a hydroxy group as a substituent, particularly a hydroxytetrazaindene compound. The heterocycle may have a substituent other than a hydroxy group. As the substituent, for example, an alkyl group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, an arylamino group, a carboxy group, an alkoxycarbonyl group,
It may have a halogen atom, an acylamino group, a cyano group, or the like. However, those having a substituent containing sulfur (for example, a mercapto group) are not preferable. This is because sulfur may also be adsorbed.

Specific examples of the tetrazaindene compound of the present invention are listed below, but the invention is not limited thereto. 1.4-Hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene 2.4-hydroxy-6-t-butyl-1,3,3a,
7-Tetrazaindene 3.4-Hydroxy-6-phenyl-1,3,3a, 7
-Tetrazaindene 4.4-hydroxy-1,3,3a, 7-tetrazaindene 5.4-methyl-6-hydroxy-1,3,3a, 7-
Tetrazaindene 6.2-methylthio-4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

7.4-Hydroxy-5-bromo-6-methyl-1,3,3a, 7-tetrazaindene 8.4-Hydroxy-6-methyl-1,2,3a, 7-
Tetrazaindene 9.4-hydroxy-6-ethyl-1,2,3a, 7-
Tetrazaindene 10.2,4-dihydroxy-6-phenyl-1,3,3
a, 7-Triazaindene 11. 4-hydroxy-6-phenyl-1,2,3,3
a, 7-Pentazaindene

The tetrazaindene compound may be added in an effective amount, but 10 ^-5 per mol of silver halide.
Mol to 10 ^-1 mol, preferably 10 ^-4 mol to 3 × 10 ^-2
The amount is more preferably 2 × 10 ⁻⁴ mol to 10 ⁻² mol, and it is particularly preferable to add it before the start of chemical ripening and to adsorb it on the surface of the silver halide. The use of these adsorptive compounds may hinder the adsorption of the sensitizing dye. That is, it is necessary for reduction sensitization, but if it remains in the silver halide after the completion of reduction sensitization, it may cause an adverse effect. In such a case, it may be treated with an ion exchange resin or an inorganic ion exchanger carrying metal ions.

The metal ion referred to in the present invention has an atomic number of 2
It refers to the first and subsequent metal ions. Preferably, from Group 4 to Group 6, Group VIII, Group VIIa, Group VIa, Ib
Group IIb, Group IIIb, Group IVb, and more preferably Group VIII, Group VIIa, Group Ib, or Group IIb. Specifically, Fe, Co, Ni, Ru, Pd, Os, I
R, Pt, Mn, Cu, Zn, Cd and the like are preferable.

The sulfate, nitrate, organic acid salt or halide salt of these metal ions is dissolved in water, a lower alcohol, a lower cyanated hydrocarbon, a ketone or the like or a mixed solvent thereof, and the ion exchange resin described below is used. Alternatively, the adsorption carrier of the present invention can be prepared by mixing and supporting it with an inorganic ion exchanger. The amount of metal ions present in the carrier of the adsorption carrier of the present invention is 0.1 to 500%, preferably 5 to 2 mol% based on the ion exchange capacity of the carrier.
00%, more preferably 10 to 100%.

The ion exchange resin referred to in the present invention is specifically a cation exchange resin (for example, Amberlite I under the trade name).
R-120; manufactured by Rohm and Haas Company, trade name Diaion SK1B, SK-102, PK-208, WK
-20; manufactured by Mitsubishi Kasei Co., Ltd. Anion exchange resin (for example, trade name DIAION SA
-21A, WA-20; manufactured by Mitsubishi Kasei Co., Ltd., trade name Dowex 1 × 8; manufactured by Dow Chemical Co., etc. Amphoteric resin and chelate resin (for example, trade name Diaion CR-10, CR-20; manufactured by Mitsubishi Kasei Co., etc.) ) Is.

Many kinds of these ion exchange resins are commercially available, and those suitable for the purpose can be easily obtained. As the resin material, not only synthetic resin (for example, styrene-divinylbenzene copolymer etc.) but also natural resin (for example, cellulose-based one)
May be used.

The inorganic ion exchanger referred to in the present invention refers to an inorganic ion exchanger having a skeleton structure of silica or silica-alumina, specifically, zeolite (eg, synthetic zeolite, A-3). , A-
4, F-9; manufactured by Wako Pure Chemical Industries, Ltd., etc. Smectite (for example, trade name Smecton; manufactured by Kunimine Industry Co., Ltd.) Montmorillonite (for example, trade name Kunipia F; manufactured by Kunimine Industry Co., Ltd.) and the like. Of these, zeolite is preferred.

The shape of the ion-exchange resin or the inorganic ion-exchanger may be granular, powdery, gel-like, film-like or the like, but one which can be easily handled may be selected. Further, the size needs to be larger than the silver halide grains used for the silver halide emulsion. This is because after the silver halide emulsion has been treated with the adsorption carrier of the present invention, these often remain in the emulsion, and there are no harmful effects even if they remain. This is because it is necessary to remove the carrier from the emulsion.

The treatment of the silver halide emulsion in the present invention with the adsorption carrier of the present invention means a step of adding the adsorption carrier to the silver halide emulsion in a batch system, stirring and mixing, and then removing the adsorption carrier by filtration, Alternatively, it refers to a step in which an adsorption carrier is continuously packed in an adsorption bed or an adsorption column and a silver halide emulsion is allowed to pass therethrough, or a step in which a silver halide emulsion is passed through a film-shaped adsorption carrier in a contact manner, Either step can be used in the present invention.

The amount of the adsorbent used depends on the performance of the carrier (eg, total exchange capacity, type of exchange group, selectivity, etc.) and shape (grain size, effective surface area, etc.), and the content of the target silver halide emulsion ( For example, it can be appropriately selected depending on the type and amount of the chemical sensitization aid. For example, in the case of batch type, 0.1 g to 100 g per 1 kg of silver halide emulsion
Can be used in the range of addition amount, and in the case of the continuous type, it can be used in the same range as in the batch type, considering the amount of the adsorption carrier with respect to the total amount of the silver halide emulsion passing through.

The processing temperature may be in the temperature range from the temperature at which the silver halide emulsion is liquefied (about 30 ° C.) to the durability temperature of the carrier, and the processing time is 1 minute for both batch type and continuous type. The above time may be set appropriately. The treatment time with the adsorption carrier in the present invention can be appropriately selected depending on the intended silver halide emulsion, but it is preferably performed after the completion of chemical ripening or just before coating, and most preferably immediately after the end of chemical ripening. Further, when the sensitizing dye is added, it is preferable that the treatment be completed before the addition of the dye is started.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemin anine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, that is, Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2
-5- to 6-membered heterocyclic nuclei such as thiotoxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanin nuclei, thiobarbituric acid nuclei can be applied.

These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. In addition to the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic ring nuclear group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensation (For example, US Pat. No. 3,743,
No. 510), a cadmium salt, and an azaindene compound. U.S. Pat. No. 3,615,613
No. 3,615,641, No. 3,617,295
No. 3,635,721, the combination is particularly useful.

The silver halide photographic emulsion used in the present invention contains various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazain Dens, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetraazaindenes), pentaazaindenes; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide can also be added. .

The light-sensitive material of the present invention is, for example, a coating aid,
One or more surfactants may be included for various purposes such as antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion and improvement of photographic characteristics (for example, development acceleration, contrast enhancement, sensitization).
The light-sensitive material of the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for various purposes such as irradiation or prevention of halation. Such dyes include oxonol dyes,
Hemioxonol dyes, styrin dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Such multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of arranging these layers can be arbitrarily selected as required. The preferred layer arrangement is from the support side in the order of red-sensitive layer, green-sensitive layer and blue-sensitive layer, blue-sensitive layer, green-sensitive layer and red-sensitive layer or blue-sensitive layer, red-sensitive layer and green-sensitive layer. . Further, an emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure to further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having different color sensitivity may be inserted between certain emulsion layers having the same color sensitivity. Under the high-sensitivity layer, in particular, the high-sensitivity blue-sensitive layer, an opposite layer made of fine grain silver halide may be provided to improve the sensitivity.

In a multilayer natural color color photographic material, it is common that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. Different combinations can be used depending on the circumstances. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Various color couplers can be used in the photographic material of the present invention. Specific examples thereof and Research Disclosure (RD) No. 17643, VII-mentioned above.
It is described in the patents described in C to G. Examples of yellow couplers include US Pat. No. 3,933,501.
No. 4,022,620, 4,326,02
4, No. 4,401,752, Japanese Patent Publication No. 58-107
39, British Patent Nos. 1,425,020 and 1,4
The compounds described in No. 76,760 are preferred.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June, 2013), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, and U.S. Pat. No. 4,500,63.
Compounds described in No. 0 and No. 4,540,654 are preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent 121,365A, US Patent 3,44
No. 6,622, No. 4,333,999, No. 4,4
The compounds described in 51,559, 4,427,767 and EP 161,626A are preferred.

Colored couplers for correcting unwanted absorption of color forming dyes are described, for example, in Research Disclosure No. 17643, Item VII-G, US Pat.
670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,
The compounds described in 004,929, 4,138,258 and British Patent 1,146,368 are preferable.
Examples of the coupler in which the color forming dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237 and British Patent No. 2,
The compounds described in 125,570, EP 96,570 and West German Patent (Publication) 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are, for example, U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and British Patent 2,102,173. No.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
Patents described in D17643, VII-F, JP-A-5
7-151944, 57-154234, 60
The compounds described in US Pat. No. 4,184,248 and US Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2,
097,140, 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, for example,
U.S. Pat. Nos. 4,283,472 and 4,338,3
No. 93, No. 4,310,618, and multiequivalent couplers, for example, JP-A-60-185950 and JP-A-62.
No. 24252, the DIR redox compound or the DIR coupler, the release coupler, for example, European Patent No. 1
No. 73,302A, a coupler that releases a dye that recolors after being released, for example, R.I. D. No. 11449, 24
241, bleach accelerator releasing couplers described in JP-A-61-2201247, such as U.S. Pat. No. 4,553,477.
Rigaton releasing couplers described in No.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. As an example,
Examples include an oil-in-water dispersion method and a latex dispersion method. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Boiling point at atmospheric pressure used in oil-in-water dispersion method is 175
Specific examples of the high boiling point organic solvent having a temperature of ℃ or higher include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylfoxyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl phenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate and trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecane amide, N, N-
Diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-te).
rt-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene)
Is mentioned. As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2 -Ethoxyethyl acetate, dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are, for example, a flexible support usually used for photographic light-sensitive materials, a flexible support such as paper, cloth or glass, earthenware, metal. Is applied to a rigid support such as. Useful as a flexible support include, for example, a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene phthalate, polycarbonate, a baryter layer or α. -Olefin polymers (e.g. polyethylene, polypropylene,
It is a paper coated or laminated with an ethylene / butene copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with, for example, the photographic emulsion layers. The surface of the support may be subjected to, for example, glow discharge, corona discharge, ultraviolet irradiation, or flame treatment before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. If necessary, for example, US Pat. Nos. 2,681,294 and 2,761,79 may be used.
1, No. 3,526,528 and No. 3,50
Multiple layers may be coated simultaneously by the coating method described in No. 8,947.

The light-sensitive material of the present invention can be applied to various color and black-and-white light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. it can. For example, by utilizing the tricolor coupler mix described in Research Disclosure No. 17123 (July 1978), or in U.S. Pat. No. 4,126,461 and British Patent 2,10.
The present invention can be applied to black-and-white light-sensitive materials such as those for X-rays by utilizing the black color couplers described in JP-A No. 2,136. The light-sensitive material of the present invention is a plate-making film such as a lith film or a scanner film,
For direct and indirect medical applications, industrial X-ray film, negative black-and-white film for photography, black-and-white photographic paper, COM-comb ordinary microfilm, silver salt diffusion transfer type photosensitive material and printout type photosensitive material Applicable.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, it is a peel-apart type or Japanese Patent Publication Nos. 46-16356 and 48-33697.
JP-A-50-13040 and British Patent 1,330,
An integrated type film unit as described in JP-A No. 524 and a peel-free type film unit as described in JP-A-57-119345 can be used.

The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous in terms of widening the processing temperature latitude. When it is used in the color diffusion transfer photographic method, it may be added to any emulsion layer in the light-sensitive material, or it may be contained as a developing solution component in a processing solution container.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the light-sensitive material can be used as the proof light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common.

A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source which emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. Further, for example, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam, a liquid crystal (LCD)
Lead zirconate titanate (PL)
It is also possible to use an exposure means in which a linear or planar light source is combined with a micro shutter array utilizing ZT). If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. As typical examples thereof, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p -Toluene sulfonate. Salts of these diamines are generally more stable than free salts, and are preferably used.

The color developing solution is, for example, a developing agent such as a pH buffering agent such as an alkali metal carbonate, borate or phosphate, bromide, iodide, benzimidazole, benzothiazole or mercapto compound. It is common to include inhibitors or antifoggants. If necessary, preservatives such as hydroxyamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dyes. Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, 1-phenyl-
Auxiliary developing agents such as 3-pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, West German Patent Application (OLS) No. 2 , 622,
The antioxidant described in No. 950 may be added to the color developer.

When the light-sensitive material of the present invention is applied to a reversal color light-sensitive material, in its developing process, black and white development is usually carried out before color development. This black and white developer contains, for example, dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents including 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

In the development processing of the light-sensitive material of the present invention, the photographic emulsion layer of the color developing agent is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. To further speed up the process, a bleach-fixing process may be performed after the bleaching process. Examples of bleaching agents include iron (III), cobalt (III), chromium (I
V), polyvalent metal compounds such as copper (II), peracids, quinones, and nitrone compounds are used. Representative bleaching agents are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates;
Nitrosophenol can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in both the independent bleaching solution and the one-bath bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators include, for example, US Pat.
893,858, West German Patent 1,290,812,
2,059,988, JP-A-53-32736,
53-57831, 53-37414, 53
-65732, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives as described in JP-A No. 50-140129; JP-B-45-8506, JP-A-52-20
832, 53-32735, and U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodides described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748.
Polyethylene oxides described in No. 430; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-42434, JP-A-49-59644, and JP-A-53
-94927, 54-57727, 55-26.
No. 506 and No. 58-163940, and compounds such as iodine and bromide. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds thioureas and a large amount of iodides, and thiosulfates are generally used. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After the bleach-fixing treatment or the fixing treatment, a washing treatment and a stabilizing treatment are usually carried out. In the washing process and stabilization process, for the purpose of preventing precipitation and saving water,
Various known compounds may be added. For example, in order to prevent precipitation, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, bactericides and preventive agents that prevent the generation of various bacteria, algae, and molds. A baiting agent, a metal salt typified by a magnesium salt, an aluminum salt, a bismuth salt, a surfactant for preventing a drying load or unevenness, and various hardeners can be added as necessary. Or, for example, by West, Photographic Science and Engineering magazine (VEWest, Phot.Sci.Eng.), Volume 6, 3.
You may add the compound as described in pages 44-359 (1965). It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, two or more tanks are subjected to countercurrent water washing,
It is common to save water. Further, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. Various compounds are added to the stabilizing bath in addition to the above-mentioned additives for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 9), Representative examples include carboxylic acids such as monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, and the like, and aldehydes such as formalin. In addition, if necessary, a chelating agent (for example, inorganic phosphoric acid,
Aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid,
Aminopolyphosphonic acid, phosphonocarboxylic acid), bactericides (for example, benzisothiazolinone, irithiazolone,
4-thiazolibenzimidazole, halogenated phenol, sulfanilamide, benzotriazole), surfactants, optical brighteners, hardeners may be used, and various additives may be used. You may use together 2 or more types.

As the membrane pH adjuster after the treatment, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate. Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). At this time, if the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be excluded. The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, though it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Nos. 3,342,597, 3,342,599, and Schiff base type compounds described in Research Disclosure Nos. 14850 and 15159, 13924, The aldol compounds described above, the metal salt complexes described in U.S. Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628, JP-A-56-6235,
56-16133, 56-59232, 56
-67842, 56-83734, 56-83.
No. 735, No. 56-83736, No. 56-89735.
No. 56, No. 56-81837, No. 56-54430, No. 56-106241, No. 56-107236, No. 5
There may be mentioned various salt type precursors described in 7-97531 and 57-83565.

The silver halide photographic light-sensitive material of the present invention contains various types of 1-, 1-, 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A-56-64339, JP-A-57-144547, JP-A-57-211147, and JP-A-5-64347.
No. 8-50532, No. 58-50536, No. 58-5
No. 0533, No. 58-50534, No. 58-5053
5 and 58-115438.

The various treatment solutions used in the present invention are from 10 ° C. to
Used at 50 ° C. A temperature of 33 ° C. to 38 ° C. is standard, but it is possible to increase the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can. Further, in order to save silver in the light-sensitive material, the processing using cobalt assist or hydrogen peroxide assist described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath. In addition, in the case of continuous processing, using a replenisher for each processing solution,
A constant finish can be obtained by preventing fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction. When the light-sensitive material of the present invention is a color paper, the bleach-fixing process as described above can be carried out in a very general manner, and also when it is a color photographic material for photographing.

[0058]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a silver halide light-sensitive material which has a remarkably high sensitivity and a low fog density, and which can be rapidly processed by reduction sensitization in the presence of a tetrazaindene compound. To do. Further, by treating this emulsion with an ion exchange resin supporting a metal ion or an inorganic ion exchanger, a silver halide photographic light-sensitive material having improved dye adsorption and excellent color sensitization can be obtained.

The effects of the present invention will be described in more detail below by showing specific examples of the present invention.

EXAMPLE A silver nitrate aqueous solution and a sodium chloride aqueous solution were simultaneously added while vigorously stirring a gelatin aqueous solution containing sodium chloride maintained at 50 ° C. to form particles.
Then, according to a conventional method, after washing with water and desalting by a flocculation method, gelatin is added to adjust the pH to 6.4 and p.
Ag was adjusted to 8.7. Thus, a monodisperse cubic silver chloride emulsion having an average grain size of about 0.5 μm was obtained. This emulsion contains 0.92 mol of silver chloride and 0.93 mol / kg.
g of gelatin is included. This is designated as emulsion (A). This emulsion is subdivided, one is 1 mol of silver halide
Then, 27 mg of thiourea dioxide was added and ripened at 60 ° C. for 60 minutes to obtain an emulsion (B). On the other hand, 6 in (A)
4-hydroxy-6-methyl-1,3,3a, 7 at 0 ° C
10 minutes after the addition of 0.40 g of tetrazaindene (hereinafter abbreviated as TAI), 27 mg of thiourea dioxide was added and ripened for 60 minutes to obtain an emulsion (C). These emulsions (A)
Emulsion (D) obtained by adding 0.40 g of TAI to (C) and (B) was coated on a cellulose acetate film under the conditions described below to obtain samples 1 to 4 which were not color-sensitized.

Next, the emulsion (C) was divided into small portions, dissolved at 40 ° C., 5 g of the adsorption carrier was added to 200 g of the silver halide emulsion as shown in Table 2, and the mixture was stirred for 10 minutes and immediately micro-sized. It was filtered with a filter to remove the adsorption carrier. The adsorbent carrier of the invention in the table-for example WA-20 /
Ni ²⁺ was obtained by mixing a 0.1 M NiCl ₂ aqueous solution with the ion exchange resin WA-20 for 1 hour and then filtering. WA
Similarly, -20 / Co ²⁺ , WK-20 / Ni ^2+, etc. are added to an aqueous solution of a corresponding metal chloride in an ion exchange resin (WA-2).
0, WK-20, etc.) were mixed and prepared. The metal ions were supported by about 40 to 60% of the total ion exchange capacity of the adsorption carrier. Sensitizing dyes were added to the emulsion (C) thus treated, the emulsion (C) treated with an adsorption carrier not supporting metal ions, the untreated emulsion (C) and the emulsion (A) for comparison. 5-Chloro-4 ', 5'-benzo-3,3'-di (3-sulfopropyl) thiacyanine triethylammonium 3.5 g / mol Silver was added and coated in the same manner as in Sample 1-4 to increase color. A felt sample 5-12 was obtained.

Coating conditions 19.1 g of a yellow coupler (ExY) and 4.4 g of a color image stabilizer (Cpd-1) and a color image stabilizer (Cpd-).
2) 1.4 g of ethyl acetate 27.2 cc and solvent (So
lv) (8.2 g) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. This was mixed and dissolved with each silver chloride emulsion and simultaneously coated with a protective layer containing gelatin and polyvinyl alcohol as acrylic modified polysynthesized and liquid paraffin as a gelatin hardening agent for each layer.
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

[0062]

[Chemical 1]

Samples 1 to 4 were exposed through a 366 nm interference filter and a light wedge, and samples 5 to 12 were exposed through a 480 nm interference filter and a light wedge (1/100 second), and then subjected to the following color development processing.

Treatment Step Temperature Time Color Development 35 ° C. 45 seconds Bleach Fixing 30-35 ° C. 45 seconds Rinse 30-35 ° C. 20 seconds Rinse 30-35 ° C. 20 seconds Rinse 30-35 ° C. 20 seconds Dry 70-80 ° C. 60 seconds The composition of each treatment liquid is as follows. Color developer water 800 ml ethylenediamine-N, N, N, N-tetramethylene phosphonic acid 1.5 g

Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulphate 5. 0 g N, N-bis (carboxymethyl) hydrazine 5.5 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g Water was added to 1000 ml pH 10.05

Bleach-fixing solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g

Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Water was added to 1000 ml pH (25 ° C.) 6.0 Rinse solution Ion-exchanged water (calcium and magnesium were 3 ppm each)
Below) these results are shown in Tables 1 and 2.

The relative sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2. Table 1 is that of sample 1 which is 100, and table 2 is the sample. That of 5 was set to 100. Further, in order to check the degree of adsorption of the dye, the absorptance at 480 nm of the coating film measured by a spectrophotometer using an integrating sphere is also shown in Table 2. 480nm
Corresponds to the absorption peak of the J-aggregate of the dye on silver halide.

[0069]

[Table 1]

[0070]

[Table 2]

As is clear from Table 1, the use of the chemical sensitization aid TAI significantly increases the intrinsic sensitivity of silver halide in the absence of a sensitizing dye, as already known, and causes fog. Is also suppressed. However, as shown in Table 2, when an attempt was made to add spectral sensitization to the sensitizing dye, the TAI used during the chemical sensitization remained in emulsion (C), which markedly hindered the adsorption of the dye (absorption rate). The sensitivity is significantly low (Sample 7). Although the sensitivity is only slightly recovered when the ion-exchange resin is used as it is (Sample 8), when the ion-exchange resin is treated with the adsorption carrier supporting the metal ion of the present invention, the TAI can be considerably removed and thus the adsorption of the dye (adsorption rate) can be improved. ) Was recovered close to emulsion (A) (Sample 5).

That is, according to the present invention, a highly sensitive emulsion was obtained, and the dye adsorption ability could be improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadaaki Tani, 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer comprises 95 mol% or more of silver chloride. And a silver halide emulsion obtained by subjecting the silver halide emulsion to reduction sensitization in the presence of a tetrazaindene compound having no substituent containing sulfur. . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion is processed by a solid substance carrying metal ions after reduction sensitization. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the metal ion is a metal ion having an atomic number of 21 or more. 4. The silver halide photographic light-sensitive material according to claim 2, wherein the solid substance carrying the metal ions is an ion exchange resin or a chelate resin.