JP3408251B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material. In particular, it relates to a silver halide photographic light-sensitive material using a silver halide emulsion having improved fog, sensitivity and gradation.

[0002]

2. Description of the Related Art A silver halide emulsion used in a silver halide photographic light-sensitive material is usually chemically sensitized with various chemical substances in order to obtain desired sensitivity, gradation and the like. Typical methods include sulfur sensitization, selenium sensitization, tellurium sensitization,
Various sensitization methods by sensitizing precious metals such as gold, reduction sensitization, and combinations thereof are known. In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, and rapid processing for accelerating the progress of development, and various improvements have been made to the sensitizing method. .

Of the above-mentioned sensitization methods, it is known that selenocarboxylic acid ester, that is, selenoester, can be used as a selenium sensitizer in the selenium sensitization method. However, relatively few examples disclose specific compounds. Among them, for example, U.S. Pat. Nos. 3,297,446, 3,297,447 and JP-B-57-2.
No. 2090 and the like describe that selenoesters are useful as selenium sensitizers, including specific compounds. However, as will be shown later by comparative data, the compounds specifically shown may show a larger sensitizing effect than the sulfur sensitization, but the occurrence of fogging is large, and it tends to be a soft tone, which causes a problem in storage. The sensitivity change tends to be large.

As described above, selenium sensitization may exhibit a greater sensitizing effect than sulfur sensitization performed in the art, but it causes a large amount of fog, and tends to cause a soft tone, resulting in sensitivity change during storage. Tend to be large. Many of the patents disclosed to date remedy these shortcomings, but still result in poor results, in particular:
Basic improvements have been eagerly desired to further suppress fogging. Further, especially when sulfur sensitization, selenium sensitization, and tellurium sensitization are used together with gold sensitization, a marked increase in sensitivity is obtained, but at the same time, fog is also increased. Compared to gold-sulfur sensitization
Since gold-selenium sensitization and gold-tellurium sensitization have particularly large increases in fog and tend to be softened, development of hard selenium sensitizers and tellurium sensitizers with less fog is strongly desired. It was

[0005]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a high-sensitivity silver halide photographic material having less fog and excellent gradation.

[0006]

The above object is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is at least one β-type. This has been achieved by a silver halide photographic light-sensitive material characterized by containing a selenolactam compound, and it has become possible to fully utilize the sensitizing effect of selenium sensitization, which was difficult with conventional techniques.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The β-selenolactam compound used in the present invention is preferably β represented by the general formula (IV).
A selenolactam compound. General formula (IV)

[0008]

[Chemical 2]

Where R₄₁Is an aliphatic group, aromatic group, or heterocycle
Represents a group and a hydrogen atom, R₄₂, R ₄₃, R₄₄, R₄₅Is water
Represents elementary atoms, aliphatic groups, aromatic groups, heterocyclic groups and silyl groups.
You

Next, the general formula (IV) will be described in detail.
It In the general formula (IV), R₄₁, R ₄₂, R₄₃, R₄₄Oh
And R₄₅The aliphatic group represented by preferably has 1 to 1 carbon atoms.
30 or more, especially linear or branched chain having 1 to 20 carbon atoms
Or cyclic alkyl group, alkenyl group, alkynyl group,
It is an aralkyl group. Here one of the branches is one of them
Or a saturated heterocycle containing more heteroatoms
It may be cyclized to form. Alkyl group,
For example, as a lukenyl group, alkynyl group, or aralkyl group
Is a methyl group, an ethyl group, an isopropyl group, t-butyl
Group, n-octyl group, n-decyl group, n-hexadecyl group
Group, cyclopropyl group, cyclopentyl group, cyclohexyl
Syl group, allyl group, 2-butenyl group, 3-pentenyl
Group, propargyl group, 3-pentynyl group, benzyl group, etc.
Is.

The aromatic groups represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ and R ₄₅ are preferably those having 5 to 30 carbon atoms, particularly 6 to 20 carbon atoms. A ring aryl group such as a phenyl group or a naphthyl group. R
_The heterocyclic group represented by ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ and R ₄₅ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a base. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, for example, pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, thienyl group, Examples thereof include furyl group and benzothiazolyl group. R ₄₂ , R ₄₃ , R ₄₄ and R ₄₅
Examples of the silyl group represented by are trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group and the like.

In the general formula (IV), R ₄₁ , R ₄₂ and R
Each group represented by ₄₃ , R ₄₄ and R ₄₅ may be substituted. The following are mentioned as a substituent. Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, n-
Propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc., alkenyl group (eg allyl group, 2-butenyl group, 3-
Pentenyl group etc.), alkynyl group (eg propargyl group, 3-pentynyl group etc.), aralkyl group (eg
Benzyl group, phenethyl group, etc.), aryl group (for example,
Phenyl group, naphthyl group, 4-methylphenyl group, etc.),
Heterocyclic groups (eg, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, butoxy group, etc.), aryloxy groups (eg, phenoxy group, 2-
Naphthyloxy group etc.), amino group (eg unsubstituted amino group, dimethylamino group, ethylamino group, anilino group etc.), acylamino group (eg acetylamino group, benzoylamino group etc.), ureido group (eg nothing Substituted ureido group, N-methylureido group, N-phenylureido group, etc., urethane group (for example, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (for example, methylsulfonylamino group, phenylsulfonylamino group) Etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, N, N-
Diethylcarbamoyl group, N-phenylcarbamoyl group etc.), sulfonyl group (eg mesyl group, tosyl group etc.), sulfinyl group (eg methylsulfinyl group, phenylsulfinyl group etc.), alkyloxycarbonyl group (eg methoxycarbonyl group) , Ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), acyl group (eg
Acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), acyloxy group (eg, acetoxy group, benzoyloxy group, etc.), phosphoric acid amide group (eg, N, N-)
Diethylphosphoric acid amide group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), arylthio group (eg phenylthio group etc.), cyano group, sulfo group,
Carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (eg trimethylammonio group), phosphonio group, hydrazino group, silyl group (eg trimethylsilyl group, triethylsilyl group, t-butyldimethyl group) Silyl group, t-butyldiphenylsilyl group, etc.) and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

More preferably in the general formula (IV), R
₄₁Is an aliphatic group or an aromatic group, and R ₄₂, R₄₃, R₄₄, R
₄₅Is a hydrogen atom, an aliphatic group, an aromatic group, or a silyl group.
Of. Most preferably in the general formula (IV), R₄₁
Is an aliphatic group, R₄₂, R ₄₄Is a hydrogen atom,
R₄₃, R₄₅Is an aliphatic group or a silyl group.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0015]

[Chemical 3]

The β-selenolactam compounds are known in the following literature, Angew. Chem. Int. Ed.
Engl. , Vol. 29, No. 5,530pp,
It can be synthesized by the method described in 1990.

So far, no specific examples have been reported in which the β-selenolactam compound is used as a selenium sensitizer. Therefore, the sensitizing action and fog of these compounds,
Although it was extremely difficult to predict other photographic effects, remarkable effects could be obtained by using the compounds of the present invention. The amount of these selenium sensitizers used in the present invention varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally 10 ^-8 to 10 ^-4 mol, preferably 1 mol to 1 mol of silver halide. Is 10 ^-7
About 10 ^-5 mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but pAg of 6 to
11, preferably 7 to 10, more preferably 7 to 9.5.
And the temperature is 40 to 95 ° C, preferably 50 to 95 ° C.
It is 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^{- About 7} to 10 ^-2 mol can be used. In the present invention, it is also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea, etc.) and rhodanines, and silver halides. About 10 ⁻⁷ to 10 ⁻² mol can be used per mol. In the present invention, it is also possible to use a reduction sensitizer in combination, and specific examples thereof include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like. To be

Further, in the present invention, it is preferable to perform selenium sensitization in the presence of a silver halide solvent. Specifically, thiocyanates (for example, potassium thiocyanate, etc.), thioether compounds (for example, US Pat.
No. 021215, No. 3271157, Japanese Patent Publication No. 58-30571, and Japanese Patent Laid-Open No. 60-13673.
No. 6, etc., especially 3,6-dithia-
1,8-octanediol, etc., tetra-substituted thiourea compounds (for example, compounds described in Japanese Patent Publication No. 59-11892, US Pat. No. 4,221,863, etc., especially tetramethylthiourea), and Japanese Patent Publication No. 60 -11341
Compounds described in Japanese Patent Publication No. 63-29727
Compounds described in JP-A-60-163
042, US Pat. No. 4,
A selenoether compound described in Japanese Patent No. 782013,
The telluroether compound, the sulfite, etc. which are described in Japanese Patent Application No. 63-173474 are mentioned. Among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is 10 ^-5 per mol of silver halide.
About 10 ^-2 mol can be used.

The silver halide emulsion used in the present invention is
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. The silver halide grains used in the present invention are
Those with regular crystal shapes such as cubes and octahedra, and irregular shapes such as spheres and plates.
lar) crystal form, or a compound form of these crystal forms. It is also possible to use a mixture of grains having various crystal forms, but it is preferable to use a regular crystal form. The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg, negative emulsion) may be used, and grains in which the latent image is mainly formed (eg, internal latent image type emulsion, pre-fogged direct reversal type emulsion) May be Preferably, the particles are such that a latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more,
Particles with an average aspect ratio of 5 or more account for 50% of the total projected area
An average grain emulsion that occupies the above or a statistical coefficient of variation (value S / d obtained by dividing standard deviation S by diameter d in the distribution represented by the diameter when the projected area is approximated by a circle) is 20.
A monodisperse emulsion having a percentage of not more than 100% is preferable. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is described by P. Glafkides, Shimmy E. Phizik.
Chimie er Physique Photographeq
ue) (published by Paul Montel, 1967), G.F.
Photographic EmulsionChemi by GFDuffin
stry) (published by Focal Press, 1966), by VL Zelikman et al., Making and Coating Photographic Emulsion (published by Focal Press, 1964), etc. It can be prepared using the method described above.

Further, when forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodancali, rodanammon,
Thioether compounds (eg US Pat. No. 3,271,1)
No. 57, No. 3,574,628, No. 3,704,130, No. 4,297,439.
No. 4,276,374, etc.), thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-10071).
No. 7, etc.) and the like can be used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer and intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. For example gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; various kinds such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Synthetic hydrophilic polymeric substances can be used. In addition to general-purpose lime-processed gelatin, acid-processed gelatin and the Japan Society for Science and Photography (Bull. Soc. Phot. Japan), No. 1
An enzyme-treated gelatin as described in pages 6, 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis ( Vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ether, vinyl polymers having a bitylsulfonyl group in the side chain, and the like) are preferable because they rapidly cure hydrophilic colloids such as gelatin and give stable photographic characteristics. N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalene sulfonate and the like) also have a fast curing rate and are excellent.

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, hemicyanine 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 nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are 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 and the like can be applied. These nuclei may have a substituent on a carbon atom. The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with 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 nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic An organic acid formaldehyde condensate (for example, those described in US Pat. No. 3,743,510), a cadmium salt, an azaindene compound and the like may be included. U.S. Pat. Nos. 3,615,613 and 3,615,64
1, No. 3,617,295, No. 3,6
The combinations described in 35,721 are particularly useful.

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

The light-sensitive material of the present invention comprises a coating aid, an antistatic agent,
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic characteristics (for example, development acceleration, hardening, sensitization). The light-sensitive material produced by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. Such dyes include oxonol dyes,
Hemioxonol dyes, styryl 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. 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 arrangement of these layers can be arbitrarily selected as required. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive, blue-sensitive layer, green-sensitive and red-sensitive layers or blue-sensitive, red-sensitive and green-sensitive. Further, an arbitrary emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity,
The graininess may be further improved as a three-layer structure. 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. A sensitivity layer may be improved by providing a reflective layer of fine grain silver halide under the high sensitivity layer, especially the high sensitivity blue sensitive layer. It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases. 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, and specific examples thereof include 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, No. 4,
326,024, 4,401,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,
Those described in Nos. 425,020 and 1,476,760 are preferable.

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 Publication EP 73,636A
U.S. Pat. No. 3,061,432, U.S. Pat. No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60.
-33552, Research Disclosure N
24230 (June 1984), JP-A-60-43.
659, US Pat. Nos. 4,500,630 and 4,540,654 are preferable. Examples of cyan couplers include phenol-type and naphthol-type couplers, and examples thereof include US Pat.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,29.
No. 6,200, No. 2,369,929, No. 2,801,171, No. 2,77.
No. 2,162, No. 2,895,826, No. 3,772,002, No. 3,75
No. 8,308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent Publication EP121,
365A, U.S. Pat. Nos. 3,446,622, 4,333,999, and 4,45.
Those described in 1,559, 4,427,767, and European Patent Publication EP161,626A are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are described, for example, in Research Disclosure No. 17643, Item VII-G, US Pat.
3,670, Japanese Patent Publication No. 57-39413,
U.S. Pat. Nos. 4,004,929 and 4,13
Those described in 8,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has an appropriate diffusibility include, for example, US Pat.
66,237, British Patent No. 2,125,570.
Those described in the specification, European Patent Publication EP96,570A, and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII to F patents, JP-A-57-151944, 57-154234, and 60-184248, and U.S. Pat. 4,24
Those described in the specification of 8,962 are preferable. Examples of the coupler that releases a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2,097,140, No. 2,131,188, and JP-A-59.
Those described in JP-A-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 41304.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 83472, No. 4338393, No. 4310618, etc., multiequivalent couplers,
JP-A-60-185950, JP-A-62-242
No. 52, etc., DIR redox compound or DIR coupler releasing coupler, European Patent No. 173302.
A coupler which emits a dye which recolors after withdrawal according to No. A,
R. D. No. 11449, No. 24241, JP-A-61-2
Bleaching accelerator releasing couplers described in JP-A-01247,
Examples thereof include ligand-releasing couplers described in US Pat. No. 4,553,477.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in oil-in-water dispersion methods are US Pat. No. 2,322,202.
No. 7 specification and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2).
-Ethylhexyl 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 phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri Dodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2
-Ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. iso- Stearyl 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-tert-octylaniline),
Hydrocarbons (eg paraffin, dodecylbenzene,
Diisopropylnaphthalene) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 50
An organic solvent having a temperature of not lower than 160 ° C and not higher than about 160 ° C can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541
No. 274 and No. 2,541,230.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are flexible supports commonly used for photographic light-sensitive materials such as plastic film, paper and cloth, or rigid support such as glass, pottery and metal. Applied to the body. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, or polycarbonate, a variator layer or an α-olefin polymer. (For example, polyethylene, polypropylene, ethylene / butene copolymer)
It is a paper or the like coated or laminated with the above. 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 photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat 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. US Patent No. 2 as required
No. 681294, No. 2761791,
No. 3526528 and No. 3508947
Multiple layers may be simultaneously coated by the coating method described in the specification or the like.

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. Research Disclosure, No.
17123 (July 1978) and the like, or by utilizing a three-color coupler mixture, or in US Pat.
26,461 and British Patent 2,102,1.
The present invention can be applied to a black-and-white light-sensitive material for X-ray and the like by utilizing the black color coupler described in the specification of No. 36 and the like. Film for film making such as lith film or scanner film, X-ray film for direct / indirect medical treatment or industrial, negative black and white film for photography, black and white photographic paper, COM or normal micro film, silver salt diffusion transfer type photosensitive material and The present invention can be applied to a printout type photosensitive material.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, it is a peel-apart type or JP-B-46-16356 and 48-33697.
Integrated type, as described in Japanese Patent Publication No. 50-13040 and British Patent No. 1,330,524, Japanese Patent Publication No. 57-11934.
A film unit of a peeling-free type as described in Japanese Patent No. 5 can be adopted. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above types of formats is advantageous for broadening the processing temperature latitude. When used in the color diffusion transfer photographic method, it may be added to any layer in the light-sensitive material, or may be contained as a developing solution component in a processing solution container before use.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits a broad radiation corresponding to the sensitivity wavelength of the light-sensitive material can be used as an illumination light source or a 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. Gas, dye solution or semiconductor laser that emits light in the wavelength range from ultraviolet to infrared
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used for developing 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. As the color developing agent, an aminophenol compound is also useful, but a P-phenylenediamine compound is preferably used, and a typical example thereof is 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-
Examples thereof include ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains a development inhibitor such as iodide, benzimidazoles, benzothiazoles or mercapto compounds or an antifoggant. If necessary, preservatives such as hydroxylamine 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, competitive couplers, nucleating agents such as sodium boron hydride, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, West German Patent Application (OLS) No. 2,622 , 95
The antioxidant described in No. 0 specification may be added to the color developer. In the development processing of a reversal color light-sensitive material, black and white development is usually performed before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 1
Known black-and-white developing agents such as 3-pyrazolidones such as -phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitrone compounds and the like are used. Ferricyanide as a typical bleaching agent; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates; manganates; nitrosophenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt,
Iron (III) diethylenetriaminepentaacetate 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 bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32736, and JP-A-53-32636
No. 57831, No. 37418, No. 53-65.
No. 732, No. 53-72623, No. 53-9
No. 5630, No. 53-95631, No. 53-
Compounds having a mercapto group or a disulfide group described in, for example, 104232, 53-124424, 53-141623, 53-28426, and Research Disclosure No. 17129 (July 1978). JP-A-50-14012
Thiazolidine derivatives as described in Japanese Patent Publication No. 9;
JP-B-45-8506 and JP-A-52-2083
No. 2, JP-A-53-32735, and US Pat. No. 3,706,561.
West German Patent 1,127,715, JP-A-58-
Iodide described in Japanese Patent No. 16235; West German Patent No. 966.
No. 410 and No. 2,748,430, polyethylene oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-424
34, 49-59644, 53-94.
No. 927, No. 54-35727, No. 55-2.
The compounds described in JP 6506 and JP 58-163940, and iodine and bromine ions can also be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858 and West German Patent 1,290,
The compounds described in JP-A No. 812 and JP-A No. 53-95630 are preferable. Further, US Pat. No. 4,552,834.
The compounds described in the specification 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. As a fixing agent, thiosulfate, thiocyanate,
Thioether compounds such as thioureas and a large amount of iodides can be used, but thiosulfate sulfate is 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, washing treatment and stabilizing treatment are usually carried out. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, bactericides and antibacterial agents that prevent the formation of various bacteria, algae, and molds. An agent, a metal salt typified by magnesimu salt or aluminum salt bismuth salt, a surfactant for preventing drying load or unevenness, and various hardeners can be added as necessary. Or West by Photographic Science and Engineering (L.
E. West, Phot. Sci. Eng.), Volume 6, 344-359
The compounds described on page (1965) and the like may be added. 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. 2 in the case of this step
Nine countercurrent baths are required. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffering agents (eg borate, metaborate, etc.) for adjusting the membrane pH (eg pH 3-9).
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Typical examples include aldehydes such as polycarboxylic acid used in combination) and formalin.
In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners and other various additives may be used, and two or more of the same or different target compounds may be used. You may use together above.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment. 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 removed. 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, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research.
Schiff base type compounds described in Disclosure Nos. 14850 and 15159, aldol compounds described in No. 13924, U.S. Pat. No. 3,719,4
92, a metal salt complex described in JP-A-53-1356.
No. 28, the urethane compounds described in JP-A-56-6235, JP-A-56-16133, JP-A-56-59232, JP-A-56-67842, JP-A-56-83734, and JP-A-56-83734. 56-83735
No. 56-83736, No. 56-8973.
5 gazette, the same 56-81837 gazette, the same 56-544.
30 publication, 56-106241 publication, 56-1.
The various salt type precursors described in JP 07236, JP 57-97531, and JP 57-83565 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-643.
39, 57-144547, 57-2.
No. 11147, No. 58-50532, No. 58
-50536, 58-50533, 5
No. 8-50534, No. 58-50535, No. 58-115438, and the like.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° 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, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 is performed. May be. If necessary, heaters in various treatment baths,
A temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided. Also,
In the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the composition of the solution. 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, it can be generally bleach-fixed if necessary and when it is a color photographic material for photographing.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Example 1 Aqueous solution 1 containing 0.05 g of potassium bromide and 30 g of gelatin kept at 75 ° C. and kept at pH 2 with nitric acid 1.
75 ml of silver nitrate aqueous solution (1M) while stirring to liter
And an aqueous potassium bromide solution (1M) were simultaneously added over 4 minutes while keeping the silver potential at 0 mV with respect to the saturated calomel electrode. Thereafter, 675 ml of an aqueous silver nitrate solution (1M) and an aqueous potassium bromide solution (1M) were added over 30 minutes while keeping the silver potential at -30 mV. After the formation of particles, desalting and washing with water were carried out by a coagulation sedimentation method using a usual polymer coagulant, and then gelatin and water were added to adjust pH to 6.4 and pAg to 8.6. The obtained silver bromide emulsion is a monodisperse octahedral emulsion having a grain diameter of 0.21 μm and a grain diameter variation coefficient of 9.5%. This emulsion was subdivided, then heated to 60 ° C., added with a sensitizer as shown in Table 1 and chemically ripened for 60 minutes so as to obtain the maximum sensitivity. Then, a magenta coupler; 3- {3- [2- (2,4-di-tert-amylphenoxy) butyrylamino) benzoylamino} -1
-(2,4,6-Trichlorophenyl) pyrazolone-5
-One, tricresyl phosphate, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene,
Simultaneously on a triacetyl cellulose film support with the addition of poly-sodium styrene sulfonate, sodium dodecyl benzene sulfonate, 1,2-bis (vinyl sulfonyl acetylamino) ethane with a gelatin protective layer containing polymethylmethacrylate particles. It was applied by the extrusion method. Exposure of these samples under an optical wedge (10 seconds)
Then, the following color development processing was performed. The density of the treated sample was measured with a green filter. The photographic properties obtained are shown in Table 1. The relative sensitivity is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value +0.2.
A was set to 100.

[0051]

[Table 1]

As is clear from the table, the conventional well-known selenium sensitizer (Comparative Compound A) has a higher sensitivity than the sulfur sensitizer (sodium thiosulfate), which has low fog but low arrival sensitivity. However, the high fog was a big drawback. On the other hand, the compound of the present invention had favorable results that the sensitivity was almost equal to or higher than that of the well-known selenium sensitizer (comparative compound A) and the fog was low. Furthermore, compared with conventionally known selenocarboxylic acid ester compounds (Comparative Compounds C and D),
The fogging was kept low. Moreover, the sensitivity was equivalent or higher, and the characteristics of the emulsion were remarkably improved.

(Color development processing method) Process processing time Processing temperature Color development 2 minutes 45 seconds 38 ° C Bleach 3 minutes 00 seconds 38 ° C Washing with water 30 seconds 24 ° C Stationary 3 minutes 00 seconds 38 ° C Washing with water (1) 30 seconds 24 ° C Washing with water (2) 30 seconds 24 ° C Stability 30 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ° C

Next, the composition of the treatment liquid will be described.   (Color developer)                                                         (Unit: g)   Diethylenetriamine pentaacetic acid 1.0   1-hydroxyethylidene-1,1-diphosphonic acid 3.0   Sodium sulfite 4.0   Potassium carbonate 30.0   Potassium bromide 1.4   Potassium iodide 1.5mg   Hydroxylamine sulfate 2.4   4- [N-ethyl-N-β-hydroxyethylamino]-   2-methylaniline sulfate 4.5   1.0 liter with water   pH 10.05

[0055]   (Bleaching solution)                                                         (Unit: g)   Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0   Ethylenediaminetetraacetic acid disodium salt 10.0   3-mercapto-1,2,4-triazole 0.08   Ammonium bromide 140.0   Ammonium nitrate 30.0   Ammonia water (27%) 6.5 ml   1.0 liter with water   pH 6.0

[0056]   (Fixer)                                                         (Unit: g)   Ethylenediaminetetraacetic acid disodium salt 0.5   Ammonium sulfite 20.0   Ammonium thiosulfate aqueous solution (700 g / l) 290.0 ml   1.0 liter with water   pH 6.7

[0057]   (Stabilizer)                                                         (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether   (Average degree of polymerization 10) 0.2   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazol-1-ylmethyl)     Piperazine 0.75   1.0 liter with water   pH 8.5

Example 2 Preparation of tabular grains 6 g of potassium bromide and 7 g of low molecular weight gelatin having an average molecular weight of 15,000 were added to 1 liter of water, and the mixture was stirred in a container kept at 55 ° C. to obtain silver nitrate. 37 mL of an aqueous solution (4.00 g of silver nitrate) and 38 nL of an aqueous solution containing 5.9 g of potassium bromide were added over 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 89 mL of a silver nitrate aqueous solution (silver nitrate 9.8 g) was added over 22 minutes. Here, 7 mL of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 100
6.5 mL of a% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added to pAg.
3 by control double jet method while keeping at 8.5
Added over 5 minutes. Next, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Average projected area diameter 1.10 μm, thickness 0.145 μm, diameter variation coefficient 1
8.5% monodisperse pure silver bromide tabular grains were obtained. After this,
Soluble salts were removed by the coagulation sedimentation method. The temperature was raised to 40 ° C again, and 30 g of gelatin and 2.3 of phenoxyethanol were used.
5 g and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and p was added with caustic soda and silver nitrate solution.
It was adjusted to H5.90 and pAg8.00. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, thiosulfonic acid compound-I

[0059]

[Chemical 4]

1 × 10 ^-5 mol / mol Ag was added, then 0.1 mol% of AgI fine particles was added, and further 0.043 mg of thiourea dioxide was added, and the mixture was kept for 22 minutes to carry out reduction sensitization. Was applied. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 2
0 mg and sensitizing dye-I

[0061]

[Chemical 5]

400 mg of was added. Further, 0.83 g of calcium chloride was added. Subsequently, 1.3 mg of sodium thiosulfate, 2.6 mg of selenium compound shown in Table 2, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-1 was completed.

Preparation of Coating Sample A coating sample was prepared by adding the following chemicals to 1 mol of silver halide of T-1 to prepare a coating solution.・ Gelatin (including Gel in emulsion) 108 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Dura Agent 1,2-bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling ratio is 230% .- Compound-I 34 mg-Compound-II 4.8 g-Compound-III 15 mg

[0064]

[Chemical 6]

[0065]

[Chemical 7]

Dye Emulsion A was added to the above coating solution so that the amount of Dye-I was 10 mg / m ² per side.

[0067]

[Chemical 8]

(1) Preparation of Dye Emulsion A Above Dye-I6
0 g and the following high boiling point organic solvents-I62.8 g, -II
62.8g and ethyl acetate 333g were melt | dissolved at 60 degreeC. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed by a dissolver at 60 ° C. for 30 minutes.
Next, 2 g of the following compound-IV and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound-IV was added to obtain a dye emulsion A.

[0069]

[Chemical 9]

The surface protective layer was prepared and prepared so that the coating amount of each component was as follows.・ Gelatin 0.78 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.080 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.015 g / m ² · Coating aid-I 0.013 g / m ² · Coating aid-II 0.045 g / m ² · Coating aid-III 0.0065 g / m ² · Coating aid-IV 0 0.003 g / m ² · Coating aid-V 0.001 g / m ² · Compound-V 1.7 mg / m ² · Compound-VI 100 mg / m ² · Polymethylmethacrylate (average particle size 3.7 μm ) 0.087 g / m ² · Proxel (adjusted to pH 7.4 with NaOH) 0.0005 g / m ²

[0071]

[Chemical 10]

Preparation of Support (1) Dye Dispersion B for Undercoat Layer
Preparation of Dye-II below was ball-milled by the method described in JP-A-63-197943.

[0073]

[Chemical 11]

Water 434 mL and Triton X-
791 mL of a 6.7% aqueous solution of 200 surfactant (TX-200) was put in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (Z
400 mL (2 mm diameter) beads of rO ₂ ) were added,
The contents were ground for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, Zr by filtration
The O ₂ beads were removed. Observing the obtained dye dispersion, the particle size of the crushed dye was 0.05 to 1.1 in diameter.
It had a wide field up to 5 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and a coating amount of the first undercoating liquid having the following composition was adjusted to 4.9 mL / m ^2. It was applied with a wire bar coater and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. Dye-I is 0.04 wt% in the polyethylene terephthalate used.
What was contained was used.・ Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 mL ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 mL ・ Distilled water 801 mL * The latex solution contains 0.4 wt% of the following compounds as an emulsifying dispersant based on the latex solids.

[0075]

[Chemical 12]

On the first undercoat layer on both sides, a second undercoat layer having the following composition was applied to each side so that the coating amount was as described below. It was applied and dried at ℃.・ Gelatin 80 mg / m ²・ Dye dispersion B (as dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Compound-VII 0.27 mg / m ²・ Mat agent Polymethylmethacrylate having an average particle diameter of 2.5 μm 2.5 mg / m ²

[0077]

[Chemical 13]

Preparation of photographic material On the prepared support, the above emulsion layer and surface protective layer were coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² .

The coated sample was exposed under a light filter and a yellow filter (1/100 second), and then X-produced by Fuji Photo Film Co., Ltd.
Processing was performed at 35 ° C. for 45 seconds with an automatic developing machine CEPROS-M for Ray, and the results shown in Table 2 were obtained. The relative sensitivity was represented by the relative value of the reciprocal of the exposure required to obtain an optical density of 2.5, and Sample 10 was set to 100.

[0080]

[Table 2]

As is apparent from the table, the compounds of the present invention produced less fog than the conventional compounds, and had favorable results in that the sensitivity of the shoulder portion in the high density portion was high.

[0082]

Industrial Applicability According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having less fog, high sensitivity, and excellent stability over time during storage.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinji Kato 550-1 Furuichiba, Gifu City, Gifu Prefecture (56) References JP-A-4-109240 (JP, A) JP-A 5-45769 (JP, A) Special Kaihei 5-100353 (JP, A) JP-A 5-134366 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/09 CAPLUS (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material, wherein at least one of the silver halide emulsion layers contains at least one β-selenolactam compound. 2. A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with at least one β-selenolactam. 3. The β-selenolactam compound is one of the following:
A contract characterized by being a compound represented by general formula (IV)
The silver halide photographic light-sensitive material according to claim 1 or 2. General formula (IV) [Chemical 1] (In the formula, R₄₁Is an aliphatic group, aromatic group, heterocyclic group or water
Represents an elementary atom, R₄₂, R ₄₃, R₄₄And R₄₅Are each
Independently hydrogen atom, aliphatic group, aromatic group, heterocyclic group or
Represents a silyl group. ) 4. In the general formula (IV), R₄₁Is an aliphatic group
Or is an aromatic group, R ₄₂And R₄₄Is an aliphatic group, aromatic
Characterized by representing a group group, a heterocyclic group or a silyl group
The silver halide photographic light-sensitive material according to claim 3.