JP3461379B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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 and sensitivity.

[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. .

Regarding the selenium sensitization method and the tellurium sensitization method among the above-mentioned sensitization methods, many techniques have been disclosed, including US Pat. No. 3,297,447 and Canadian Patent No. 800958.

Selenium sensitization may show a larger sensitizing effect than sulfur sensitization, but fogging is large, and
There is a tendency that the tone tends to be soft and the sensitivity changes greatly during storage. Many of the patents disclosed so far improve these drawbacks, but the results are still unsatisfactory, and a basic improvement for further suppressing the occurrence of fog has been eagerly desired. When gold sensitization is used in combination with sulfur sensitization, selenium sensitization, and tellurium sensitization, a marked increase in sensitivity can be obtained, but at the same time, fog also increases. Compared with gold-sulfur sensitization, gold-selenium sensitization and gold-tellurium sensitization have a particularly large increase in fog and tend to soften, so a hard selenium sensitizer with less fog and tellurium sensitization. The development of agents was still strongly desired.

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, there are relatively few examples in which specific compounds are disclosed. Among them, for example, U.S. Pat. Nos. 3,297,446, 3,297,447, and Japanese Patent Publication No. 57-22090 describe that selenoesters are useful as selenium sensitizers, with specific compounds. However,
As will be shown later in the comparative data, the compounds specifically shown may show a larger sensitizing effect than sulfur sensitization, but the fog is large, the tone tends to be softened, and the sensitivity changes greatly during storage. Tends to.

Further, JP-A-5-303157 discloses dicarbamoyl telluride compounds as tellurium sensitizers. All of these compounds have two carbonyl groups or imino groups (-C (= NR) on the tellurium atom.
-, Where R represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom) is bonded, and does not disclose a tellurium sensitizer of the type found by the present invention.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material with less fog.

[0008]

The above object has at least one silver halide emulsion layer on a support and contains at least one compound represented by the following general formula (I) or (II). It was achieved by a silver halide photographic light-sensitive material. General formula (I)

[0009]

[Chemical 5]

In the formula, R ₂ is an aliphatic group, an aromatic group, a heterocyclic group, COR ₃ , COOR ₄ , CONR ₅ R ₆ , C (= X
₂ ) represents R ₇ , wherein R ₁ and R ₇ are a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₈ R ₉ , OR ₁₀ , SR ₁₁
Represents X ₁ and X ₂ represent NR ₁₂ and N ⁺ R ₁₃ R ₁₄ Y ⁻ . R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ ,
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y ⁻ represents an anion. General formula (II)

[0011]

[Chemical 6]

In the formula, R ₂₂ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂₁ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₂₃ R ₂₄ , OR ₂₅ or SR. Represents ₂₆ . X ₂₁ is NR
^{_{27, N + R 28 R 29}} Y - represents a. R ₂₃ , R ₂₄ , R ₂₅ ,
R ₂₆ , R ₂₇ , R ₂₈ , and R ₂₉ represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y ⁻ represents an anion.

Next, the general formula (I) will be described in detail. In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R
_The aliphatic group represented by ₁₃ and R ₁₄ preferably has 1 to 30 carbon atoms, and particularly has 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group, alkenyl group, alkynyl group, or aralkyl group. Here the branched ones may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group and cyclopentyl group. Group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group and the like.

In the general formula (I), R ₁ , R ₂ , R
₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
The aromatic group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is preferably an aromatic group having 5 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms. There are, for example, a phenyl group and a naphthyl group. In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
_The heterocyclic group represented by ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a saturated or unsaturated heterocyclic group. 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. In the general formula (I), the anion represented by Y is a halogen anion such as chloride ion, bromide ion, or iodide ion, a carboxylate anion such as acetate ion, or a sulfonic acid such as benzenesulfonate ion. anion,
In addition, inorganic anions such as perchlorate anions can be used. Further, in the general formula (I), R ₁ , R ₂ ,
_{R 3, R 4, R 5} , R 6, R 7, R 8, R 9, R 10, R
Each group represented by ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ 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 (eg, phenyl group, naphthyl group, 4-methylphenyl group, etc.), heterocyclic group ( For example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 2-naphthyloxy group, etc.) ), An amino group (for example, an unsubstituted amino group, a dimethylamino group, an ethylamino group, an anilino group, etc.), Shiruamino group (e.g., acetylamino group, benzoylamino group, etc.), a ureido group (e.g., unsubstituted ureido group, N- methylureido group, N-
Phenylureido group etc.), urethane group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), sulfonylamino group (eg methylsulfonylamino group, phenylsulfonylamino group etc.), sulfamoyl group (eg unsubstituted sulfamoyl group) , N, N-
Dimethylsulfamoyl group, N-phenylsulfamoyl group and the like), carbamoyl group (for example, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group and the like), sulfonyl group (for example, 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 (for example, N, N-diethylphosphoric acid amide group, etc.), alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, etc.), cyano group,
A sulfo group, a carboxy group, a hydroxy group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group (for example, a trimethylammonio group, etc.), a phosphonio group, a hydrazino group and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), R ₁ and R ₂ , R ₅ and R ₆ , R ₈ and R ₉ , R ₁₃ and R ₁₄ and X ₁ and X ₂ are optionally bonded to each other to form a ring. Good. In the general formula (I), preferably R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, NR ₈ R ₉ , OR ₁₀ or SR ₁₁ , and R ₂ represents an aliphatic group, an aromatic group or a heterocyclic group. The group C (= X ₂ ) R ₇ represents X
₁ , X ₂ represents NR ₁₂ , N ⁺ R ₁₃ R ₁₄ Y ⁻ , and R ₁₂ , R
₁₃ and R ₁₄ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and Y ⁻ represents an anion. More preferably in the general formula (I), R ₁ is an aromatic group, NR ₈ R
₉ and OR ₁₀ , R ₂ represents an aliphatic group or a heterocyclic group,
X ₁ is ^{_{NR 12, N + R 13 R}} 14 Y - represents, R _12, R _13,
And R ₁₄ represent an aliphatic group or an aromatic group, and Y ⁻ represents an anion. Most preferably in the general formula (I), R
₁ represents an aromatic group, NR ₈ R ₉ , R ₂ represents an aliphatic group, X ₁ represents NR ₁₂ , N ⁺ R ₁₃ R ₁₄ Y ⁻ , R ₁₂ and R
_13, and R ₁₄ is an aliphatic group (e.g., 3-Okisobuchi Le group having an electron-withdrawing group at β-position, 3-oxo-cyclohexyl group, 2-cyanoethyl, 2-alkoxycarbonylethyl group, 2-alkylsulfonyl-ethyl Group) and an aromatic group, and Y ⁻ represents an anion.

Next, the general formula (II) will be described in detail.
It In the general formula (II), R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four},
R_{twenty five}, R₂₆, R₂₇, R₂₈, And R₂₉Represented by
The group, the aromatic group and the heterocyclic group are represented by R in the general formula (I). ₁ ,
R₂ , R₃ , R_Four , R_Five , R₆ , R₇ , R₈ , R₉ , R
_Ten, R₁₁, R₁₂, R ₁₃, And R₁₄Represented by
It has the same meaning as a group, an aromatic group and a heterocyclic group. Also, the general formula
In (II), Y^-The anion represented by
Y in (I) ^-Is equivalent to the anion represented by
It In the general formula (II), preferably R_{twenty one}Is aliphatic
Group, aromatic group, heterocyclic group, NR_{twenty three}R_{twenty four}, OR_{twenty five}, SR₂₆
Represents R_{twenty two}Represents an aliphatic group, an aromatic group, or a heterocyclic group,
X_{twenty one}Is NR₂₇, N⁺R₂₈R₂₉Y^-Represents R_{twenty three}, R_{twenty four},
R_{twenty five}, R₂₆, R₂₇, R ₂₈, And R₂₉Is a hydrogen atom, fat
Represents an aliphatic group, an aromatic group, or a heterocyclic group, Y^-Is an anion
Represent More preferably in the general formula (II), R_{twenty one}Is
Aromatic group, NR_{twenty three}R_{twenty four}, OR _{twenty five}Represents R_{twenty two}Is aliphatic
A heterocyclic group, X_{twenty one}Is NR₂₇, N⁺R₂₈R₂₉Y^-
Represents R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₇, R₂₈, And R
₂₉Represents an aliphatic group or an aromatic group, and Y^-Represents anion
You

Even more preferably in the general formula (II), R ₂₁ represents an aromatic group, NR ₂₃ R ₂₄ , R ₂₂ represents an aliphatic group, X ₂₁ represents NR ₂₇ , N ⁺ R ₂₈ R ₂₉ Y ^- represents a, R
₂₃ , R ₂₄ , R ₂₇ , R ₂₈ , and R ₂₉ represent an aliphatic group or an aromatic group, and Y ⁻ represents an anion. Most preferably in formula (II), R ₂₁ is an aromatic group, an NR ₂₃ R _24, R ₂₂ is an aliphatic group (e.g., 3-Okisobuchi Le group having an electron attractive group in position beta, 3-oxo Cyclohexyl group,
2-cyanoethyl, 2-alkoxycarbonylethyl group, a 2-alkyl sulphonyl ethyl), X ₂₁ is ^{_{NR 27, N + R 28 R}} 29 Y - _{represents, R 23, R 24, R} 27,
R ₂₈ and R ₂₉ represent an aliphatic group or an aromatic group, and Y ⁻
Represents an anion. In the present invention, the compound more preferably used is the compound represented by the general formula (I).
Specific examples of the compound of the present invention are shown below, but the compound of the present invention is not limited thereto.

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

The compounds represented by the general formulas (I) and (II) are known in the following literature, S. Patai, Z. Rappop.
ort, The Chemistry of Organic Selenium and Tellurium Compounds (The Chem
istry of Organic Selenium and Tellurium Compounds)
, Volume 1 (1986), Volume 2 (1987)
), D. Liotta, Organoselenium Chemistry, (1987),
KJ Irgolic, The Organic Chemistry of Tellurium
, (1974), and J.Chem.Soc.Chem.Commu
n., 505, (1977), Z.Chem., vol.14,228, (1974), Z.Chem., vo
It can be synthesized according to the method described in l.15, 66, (1975), etc.

So far, compounds of the general formulas (I) and (II) have been combined.
Specific example in which the compound was used as a selenium sensitizer or tellurium sensitizer
No examples have been reported. So depending on these compounds
Predicting sensitization, fog, and other photographic effects
Was extremely difficult to achieve, but using the compounds of the present invention
With, the remarkable effect could be obtained. These books
The amount of selenium sensitizer and tellurium sensitizer used in the invention is
Selenium compounds, tellurium compounds, silver halide grains used
Generally halogenated, although it varies depending on factors such as the child and chemical aging conditions.
10 per mole of silver^-8-10^-FourMol, preferably 10^-7~
10 ^-FiveUse molar amounts. Article of chemical sensitization in the present invention
The matter is not particularly limited, but pAg is 6 to 1
1, preferably 7 to 10, more preferably 7 to 9.5
And the temperature is 40 to 95 ° C., preferably 50 to 8
It is 5 ° 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 specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivative, borane compound, silane compound, polyamine compound, Etc.

In the present invention, selenium sensitization is preferably carried out 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. 58-3
No. 0571, JP-A-60-136736 and the like, particularly compounds such as 3,6-dithia-1,8-octanediol) and tetra-substituted thiourea compounds (for example, JP-B-59-1).
1892, U.S. Pat. No. 4,221,863, etc., particularly tetramethylthiourea, etc.), and thione compounds described in JP-B-60-11341, JP-B-63.
-29727, mercapto compounds, JP-A-60
Examples include the mesoionic compound described in -163042, the selenoether compound described in U.S. Pat. No. 4,782,013, the telluroether compound described in Japanese Patent Application No. 63-173474, and a sulfite. Among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is 10 ^-5 to 10 ^-2 per mol of silver halide.
A molar amount 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), GFDuffin, Photographic EmulsionChe
mistry) (Focal Press, 1966), buoy
Making by VLZelikman et al.
It can be prepared by the method described in Making and Coating Photographic Emulsion (Focal Press, 1964) and the like.

In order to control the growth of the silver halide grains at the time of forming the silver halide grains, a silver halide solvent such as ammonia, rhodancali, rhodanammon,
Thioether compounds (eg US Pat. No. 3,271,1)
No. 57, No. 3,574,628, No. 3,704.
No. 130, No. 4,297,439, No. 4,27.
6,374) and thione compounds (for example, JP-A-53)
No. 144319, No. 53-82408, No. 55-7.
7737), amine compounds (for example, JP-A-54-
No. 100717) 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.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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 of 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.

The photosensitive material of the present invention may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic photosensitive 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-naphthalenesulfonate 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 a combination thereof may be used, 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 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, an azaindene compound, and the like. U.S. Pat. No. 3,615,6
No. 13, No. 3,615, 641, No. 3,617, 29
The combinations described in No. 5 and No. 3,635,721 are particularly useful.

The silver halide photographic emulsion used in the present technology contains various compounds for the purpose of preventing fog during the production 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,
Azo dyes are preferably used, in addition to these, 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, 4,326,02
4, No. 4,401,752, Japanese Patent Publication No. 58-107
39, British Patent Nos. 1,425,020 and 1,4
Those described in No. 76,760 are preferable.

As the magenta coupler, 5-pyrazolone type and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,8.
97, European Patent 73,636, US Patent 3,0.
61,432, 3,725,067, Research Disclosure No. 24220 (6 June 1984).
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
Nos. 4,540,654 are preferable. Examples of cyan couplers include phenol-type and naphthol-type couplers, and examples thereof include US Pat.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308,
No. 4,334,011, No. 4,327,173
, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, US Patent No. 3,446,622.
No. 4,433,999, 4,451,55
9, No. 4,427,767, European Patent 161,
Those described in No. 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. No. 4,16.
Those described in 3,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, 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. No. 4,366,237, British Patent 2,125,570, and European Patent 96,57.
Those described in No. 0 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282 and British Patent No. 2,102,173.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, Patents described in paragraphs VII to F, JP-A-5
7-151944, 57-154234, 60
Those described in US Pat. No. 4,184,248 and US Pat. No. 4,248,962 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patents 2,097,140 and 2,131,1.
88, JP-A-59-157638 and JP-A-59-170.
Those described in No. 840 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 US Pat. No. 27,834, US Pat.
No. 72, No. 4338393, No. 4310618 and the like, multiequivalent couplers, JP-A-60-185950.
DIR redox compounds or DIR coupler releasing couplers described in JP-A No. 62-24252 and the like, couplers releasing a dye that restores color after separation described in EP 173302A, R.I. D. No. 11449, 2424
1, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

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, etc. Specific examples of the high-boiling 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 (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Screw (2,
4-di-t-amylphenyl) phthalate, bis (2,2
4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl 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-diethyldodecaneamide, 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 (eg, , N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, 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. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are a flexible support usually used for photographic light-sensitive materials, such as a flexible support such as plastic film, paper and cloth, or a 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. 3526
Multiple layers may be coated at the same time by the coating methods described in No. 528 and No. 3508947.

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.
The present invention can be applied to a black-and-white light-sensitive material for X-rays or the like by utilizing the black color-forming coupler described in No. 26,461 and British Patent No. 2,102,136. 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 printing paper, CO
The present invention can be applied to M or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

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 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 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. 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 buffer 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 may be added to the color developing solution.

In the development processing of the reversal color light-sensitive material, black and white development is usually carried out and then color development is carried out. 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, 2,059,988, JP 53-32736, 53-57831, 37
No. 418, No. 53-65732, No. 53-72623.
No. 53, No. 53-95630, No. 53-95631, No. 53-104232, No. 53-124424, No. 5
No. 3-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; and thiazolidine derivatives as described in JP-A No. 50-140129; JP-B-45-8506.
No. 52-20832 and 53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, JP-A-58.
No. 16235, iodide; West German Patent No. 966,4.
No. 10 and No. 2,748,430; polyethylene oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434, JP-A-49434
-59644, 53-94927, 54-35.
727, 55-26506 and 58-163.
The compounds described in No. 940 and iodine and bromide ions can also be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858 and West German Patent Nos. 1,29.
Compounds described in JP-A No. 0,812 and JP-A-53-95630 are preferable. 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, 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. In the case of this step, a countercurrent bath of 2 to 9 tanks is 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 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 aldehydes such as monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids 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, indaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base type compounds described in No. 3,342,599, Research Disclosure 14850 and No. 15159, aldol compounds described in No. 13924, Metal salt complexes described in U.S. Pat. No. 3,719,492, urethane compounds described in JP-A No. 53-135628, JP-A Nos. 56-6235 and 56-
16133, 56-59232, 56-678.
No. 42, No. 56-83734, No. 56-83735.
No. 56, No. 56-83736, No. 56-89735, No. 56-81837, No. 56-54430, No. 56-.
106241, 56-107236, 57-9.
Various salt type precursors described in, for example, No. 7531 and No. 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. Typical compounds are JP-A Nos. 56-64339, 57-144547 and 5
7-211147, 58-50532, 58-
No. 50536, No. 58-50533, No. 58-505.
34, 58-50535 and 58-1154.
No. 38 and the like.

Various treatment liquids 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 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. Further, 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 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, it can be generally bleach-fixed if necessary and when it is a color photographic material for photographing.

[0063]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Example 1 0.05 g of potassium bromide and 30 g of gelatin kept at 78 ° C
While stirring in 1 liter of an aqueous solution containing g and kept at pH 2 with nitric acid, 75 ml of an aqueous silver nitrate solution (1M) and an aqueous potassium bromide solution (1M) were simultaneously added, while the silver potential was kept at 0 mV with respect to a saturated calomel electrode. Added in minutes. After that, 675 ml of an aqueous silver nitrate solution (1M) and an aqueous solution of potassium bromide (1M) were further added while keeping the silver potential at -30 mV.
Added in minutes. 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 had a grain diameter of 0.28 μm,
It is a monodisperse octahedral emulsion having a variation coefficient of grain diameter of 9%.
This emulsion was divided into small portions, heated to 60 ° C., and a sensitizer was added as shown in Table 1 to chemically ripen the emulsion so as to obtain the maximum sensitivity. After that, 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, sodium poly-styrenesulfonate, sodium dodecylbenzenesulfonate, 1,2-bis (vinylsulfonylacetylamino) ethane were added together with a gelatin protective layer containing polymethylmethacrylate particles. , Was coated on a triacetyl cellulose film support by the simultaneous extrusion method. These samples were exposed under a light wedge (10 seconds) and subjected to the following color development processing. The density of the treated sample was measured with a green filter. The photographic properties obtained are shown in Table 1. The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and the value of Sample 1A was set to 100.

[0064]

[Table 1]

As is clear from the table, the fog is low,
Compared to the sulfur sensitizer (sodium thiosulfate), which has a low arrival sensitivity, the conventional well-known selenium sensitizer (Comparative Compound A) can provide high sensitivity, but has a big problem of high fog. . 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. Further, compared with the conventionally known selenocarboxylic acid ester compound (Comparative compound C), the fog was suppressed to be 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

[0068] (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

[0069] (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

[0070] (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 average molecular weight of 15 in 1 liter of water.
Thousands of low molecular weight gelatin (7 g) were added, and 37 ml of an aqueous solution of silver nitrate (4.00 g of silver nitrate) and 38 cc of an aqueous solution containing 5.9 g of potassium bromide were added to the container maintained at 55 ° C. for 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C and 89 cc of silver nitrate aqueous solution (silver nitrate) was added.
9.8 g) was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 6.5 cc of 100% 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 pA.
35 by the control double jet method while maintaining g8.5
Added over 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 1.10μ
Thus, monodisperse pure silver bromide tabular grains having m, thickness of 0.145 μm and variation coefficient of diameter of 18.5% were obtained. After this, soluble salts were removed by the coagulation sedimentation method. The temperature is raised to 40 ℃ again and gelatin 30g is added.
Then, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 5.9 and pAg 8.0 with caustic soda and silver nitrate solution.
This emulsion was subjected to chemical sensitization while being kept at 56 ° C while stirring. First, thiosulfonic acid compound-I

[0072]

[Chemical 10]

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 held for 22 minutes to carry out reduction sensitization. Next, 4-hydroxy-6-methyl-1,
20 mg of 3,3a, 7-tetrazaindene and sensitizing dye-I

[0074]

[Chemical 11]

400 mg was added. Furthermore, 0.83 g of calcium chloride was added. Continued sodium thiosulfate 1.3
mg, selenium compounds 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 T-1 silver halide 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 ・ Hardener 1,2-bis (Vinylsulfonylacetamide) ethane Adjust the amount added so that the swelling rate is 230% .- Compound-I 34 mg-Compound-II 4.8 g-Compound-III 15 mg

[0077]

[Chemical 12]

[0078]

[Chemical 13]

Dye-I was applied to one side of the above coating solution.
Dye Emulsion A was added to give 10 mg / m ² .

[0080]

[Chemical 14]

(1) Preparation of Dye Emulsion A 60 g of the above dye-I and the following high boiling organic solvent-I 62.8
g, -II 62.8 g and ethyl acetate 333 g were dissolved at 60 ° C. Next, a 5% aqueous solution of sodium dodecyl sulfonate
65 cc, 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, the following compound
2 g of IV and 6 liters of water were added, and the temperature was lowered to 40 ° C.
Next, Asahi Kasei Ultrafiltration Lab Module ACP105
0 was concentrated until the total amount became 2 kg, and 1 g of the following compound-IV was added to obtain a dye emulsion A.

[0082]

[Chemical 15]

The surface protective layer was prepared and prepared so that each component had the following coating amount.・ 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 Auxiliary agent-I 0.013 g / m ² , coating auxiliary agent-II 0.045 g / m ² , coating auxiliary agent-III 0.0065 g / m ² , coating auxiliary agent-IV 0.003 g / m ² , coating auxiliary agent-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

[0084]

[Chemical 16]

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

[0086]

[Chemical 17]

434 ml of water and 791 ml of 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO ₂ ) beads 400ml
(2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming,
The ZrO ₂ beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye is 0 diameter.
It has a wide field from 05 to 1.15 μm, and the average particle size was 0.37 μm. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more.
Thus, Dye Dispersion B was obtained. (2) Preparation of support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 175 μm and biaxially stretched, and a first undercoating liquid having the following composition was applied to a wire so that the coating amount was 4.9 cc / m ^2. It was applied with a bar coater and dried at 185 ° C for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used is a dye-
I containing 0.04 wt% was used. -Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 cc-2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 cc-Distilled water 801 cc * Latex solution contains 0.4 wt% of the following compounds as emulsifying dispersant based on latex solids

[0088]

[Chemical 18]

On the above-mentioned first undercoat layer on both sides, a second undercoat layer having the following composition was applied on 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 Average particle size 2.5 μm polymethylmethacrylate 2.5 mg / m ²

[0090]

[Chemical 19]

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 amount of coated silver per side is 1.
It was set to 75 g / m ² .

The coated sample was exposed under a light filter and a yellow filter (1/100 seconds), and 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 amount required to obtain an optical density of 2.5, and the value of Sample 10 was set to 100.

[0093]

[Table 2]

As is clear from the table, the compounds of the present invention produced less fog than the conventional compounds, and the preferable results were that the sensitivity of the shoulder of the high density portion was high.

Example 3 1 liter of an aqueous solution containing 25 g of gelatin and 2.3 g of NaCl was maintained at 50 ° C. with stirring and an AgNO ₃ aqueous solution (1
Na) containing M) and K ₃ IrCl ₆ (5 × 10 ⁻⁷ mol)
1 Aqueous solution (1M) was simultaneously added over 80 minutes to obtain a cubic silver chloride emulsion having a grain size of 0.5 μm.

Then, after washing and desalting with a usual flocculation method using a polymer flocculant, 76 g of gelatin and water were added, and the pH was adjusted to 6.2 at 40 ° C. and the pAg was adjusted to 7.5. It was After subdividing the emulsion, the sensitizing dye was added and then sodium benzenethiosulfonate (50
× 10 ⁻⁵ mol / mol Ag), and

[0097]

[Chemical 20]

The compounds shown in Table 3 were optimally chemically aged at 56 ° C. After that, gelatin, water, and yellow coupler

[0099]

[Chemical 21]

Color image stabilizer

[0101]

[Chemical formula 22]

And a stabilizer; 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene antifoggant; 1- [3- (3-methylureido) phenyl] -5-mercaptotetrazole latent Image stabilizer; N-allylbenzothiazolium bromide coating aid; Sodium dodecylbenzene sulphonate hardener; 2,4-dichloro-6-hydroxy-s-triazine sodium salt is added sequentially and laminated on both sides with polyethylene. A sample was obtained by coating with a gelatin protective layer on the prepared paper support.

The sample was exposed under a light wedge (1/10 seconds), and the following developing treatment was carried out to obtain the results shown in Table 3. However, the relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to give the density of the fog value + 0.5, and that of Sample 20 was set to 100.

(Color developer formulation) 33 ° C. 60 seconds Development water 800 cc Diethylenetriamine pentaacetic acid 1.0 g Sodium sulfite 0.2 g N, N-diethylhydroxylamine 4.2 g Potassium bromide 0.01 g Sodium chloride 1.5 g Triethanol Amine 8.0 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g 4,4-diaminostilbene optical brightener (Sumitomo Chemical ( Whitex4) 2.0g Water is added and the total amount is 1000cc in KOH pH10.25 (bleach-fixing formulation) 35 ° C 45 seconds Ammonium thiosulfate (54% by weight) 150ml Sodium sulfite 15g NH ₄ [Fe (III) (EDTA)] ] 55 g EDTA.2Na 4 g glacial acetic acid 8.61 g Total amount 1000 cc (pH 5.4) (Rinse solution formulation) 35 ° C. 90 seconds EDTA.2Na.2H ₂ O 0.4 g Water was added to total amount 1000 cc (pH 7.0)

[0105]

[Table 3]

As is apparent from the table, the compounds of the present invention are
As a result, the fog is less likely to occur and the sensitivity is higher than that of the conventional compound, which is preferable. Example 4 Samples 401 and 402, which are multilayer color light-sensitive materials, were prepared in the same manner as in Example 6 of Japanese Patent Application No. 4-226153.
In Sample 401, the emulsions A, B, C, D, E and F used as selenium sensitizers when sensitizing gold, sulfur and selenium were:
Comparative compound A of Example 1 was used. On the other hand, in Sample 402, Emulsions A, B, C, D, and F used the same comparative compound A as in Sample 401, but Emulsion E was chemically sensitized with the selenium sensitizer 1-18 of the present invention. I felt.

Samples 401 and 402 were exposed through a continuous wedge at a color temperature of 4800K for 1/100 seconds and then subjected to the same color development process as in Example 6 of Japanese Patent Application No. 4-226153 to measure the optical density. Sample 401
And sample 402 under conditions of 50 ° C. and 80% relative humidity.
Samples stored for days were similarly exposed and processed. Change in fog density before and after storage of red-sensitive layer for 7 days, and fog +
Table 4 shows the change in logarithm (ΔS) of the exposure dose required to obtain an optical density of 0.2. As is clear from Table 4, the compound of the present invention gives favorable results that changes in fog and changes in sensitivity during storage under high temperature and high humidity are small.

[0108]

[Table 4]

[0109]

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 front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/09 G03C 1/34

Claims (4)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₂ is an aliphatic group, an aromatic group, a heterocyclic group, or COR
₃ , COOR ₄ , CONR ₅ R ₆ , C (= X ₂ ) R ₇ are represented, and R ₁ and R ₇ are a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₈ R ₉ , OR ₁₀ , Represents SR ₁₁ . X
₁ , X ₂ represents NR ₁₂ , N ⁺ R ₁₃ R ₁₄ Y ⁻ . R ₃ , R
₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ , and R ₁₄ represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y ⁻ represents an anion. 2. 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 characterized in that at least one of said silver halide emulsion layers contains a silver halide emulsion chemically sensitized with at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₂ is an aliphatic group, an aromatic group, a heterocyclic group, or COR
₃ , COOR ₄ , CONR ₅ R ₆ , C (= X ₂ ) R ₇ are represented, and R ₁ and R ₇ are a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₈ R ₉ , OR ₁₀ , Represents SR ₁₁ . X
₁ , X ₂ represents NR ₁₂ , N ⁺ R ₁₃ R ₁₄ Y ⁻ . R ₃ , R
₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ , and R ₁₄ represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y ⁻ represents an anion. 3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing at least one compound represented by the following general formula (II). General formula (II): In the formula, R ₂₂ represents an aliphatic group, an aromatic group or a heterocyclic group, R _22
21 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₂₃
It represents R ₂₄ , OR ₂₅ , and SR ₂₆ . X ₂₁ is NR ₂₇ , N ⁺ R ₂₈
Represents R ₂₉ Y ⁻ . R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ ,
R ₂₈ and R ₂₉ are each a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, and Y ⁻ represents an anion. 4. 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 a silver halide emulsion chemically sensitized with at least one compound represented by the following general formula (II). General formula (II): In the formula, R ₂₂ represents an aliphatic group, an aromatic group or a heterocyclic group, R _22
21 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₂₃
It represents R ₂₄ , OR ₂₅ , and SR ₂₆ . X ₂₁ is NR ₂₇ , N ⁺ R ₂₈
Represents R ₂₉ Y ⁻ . R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ ,
R ₂₈ and R ₂₉ are each a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, and Y ⁻ represents an anion.