JPH0635104A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve after color in development processing and to enhance sensitivity by incorporating each specified plural compounds. CONSTITUTION:The silver halide photographic sensitive material contains at least one of the compounds represented by formula I and also the compounds represented by formula II, and in formulae I and II, R<1> is -(CH2)r-CONHSO2-R<3> or -(CH2)S-SO2NHCO-R<4> or the like; each of R<3> and R<4> is alkyl, alkoxy, or the like; each of r and s is an integer of l-5: R<2> is same as R<1> or different from it; each of Z<1>-Z<3> is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; each of L1-L5 is a methine group; n1 is 0, 1, or 2; X1 is an anion; k1 is a number for neutralizing an electric charge in the molecule; each of p1 and q1 is 0 or 1; Y<1> is a nonmetallic atomic group necessary to form a 5- or 6-membered acid ring: each of R<7> and R<8> is alkyl except a group represented by R<1>; v1 is 0 or 1; and w1 is 0-3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having improved residual color and sensitivity during development processing.

[0002]

2. Description of the Related Art With the recent rapid development process and the addition of large amounts of sensitizing dyes, the sensitizing dyes contained in silver halide light-sensitive materials are not completely dissolved during the processing, and coloring occurs in the light-sensitive materials. The problem of leaving (so-called residual color) is growing. Conventionally, such sensitizing dyes having less residual color are disclosed in Japanese Examined Patent Publication Nos. 51-1126 and 51-4105, and British Patent No. 1
Although those described in, for example, No. 333013 have been studied, sufficient results have not been obtained in terms of compatibility of sensitivity and residual color.

[0003]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material capable of achieving both residual color and sensitivity during development processing.

The above object of the present invention is to provide at least one compound represented by the following general formula (I) and a compound represented by the following general formula (II) or general formula (IV). It has been achieved by a silver halide photographic light-sensitive material characterized by containing at least one kind. General formula (I)

[0004]

[Chemical 5]

Where R¹Is-(CH₂)_r-CONHSO
₂-R³,-(CH₂)_s-SO₂NHCO-R^Four,-
(CH₂)_t-CONHCO-R^Five, Or-(CH₂)_u
-SO ₂NHSO₂-R⁶Represents Where R³,
R^Four, R^Five, Or R⁶Is an alkyl group, an alkoxy group,
Or represents an amino group, and r, s, t, or u is 1
Represents an integer from 5 to 5. R²Is R¹Synonymous with or
R¹Represents an alkyl group different from. Z¹And Z²Is
May be the same or different and may have a 5- or 6-membered heterocycle
Represents the group of non-metal atoms required to form. L₁,
L₂, Or L₃Represents a methine group, n₁Is 0, 1
Or represents 2. X₁Represents an anion, k₁Is a minute
It represents the number needed to adjust the charge in the child to zero. p₁
Or q₁Represents 0 or 1. General formula (II)

[0006]

[Chemical 6]

In the formula, Z ³ represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle. Y ¹ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered acidic nucleus. R ⁷ and R ⁸ represent alkyl groups other than those defined for R ¹ . v ₁ represents 0 or 1. w ₁ is 0,
Represents 1, 2 or 3. L ₄ and L ₅ have the same meaning as L ₁ . General formula (IV)

[0008]

[Chemical 7]

In the formula, Z ⁶ has the same meaning as Z ³ , and Y ² is Y
Synonymous with ¹ . R ¹¹ or R ¹² represents an alkyl group, but at least one of them represents a substituent defined by R ¹ . L ₉ and L ₁₀ have the same meaning as L ₁ . v ₂ has the same meaning as v ₁ and w ₂ has the same meaning as w ₁ . Further, the above object of the present invention is to include at least one compound represented by the following general formula (III) and at least one compound represented by the above general formula (IV). It was also achieved by the material. General formula (III)

[0010]

[Chemical 8]

In the formula, Z ⁴ and Z ⁵ have the same meaning as Z ¹ . R ⁹ and R ¹⁰ represent alkyl groups other than those defined for R ¹ . L ₆ , L ₇ , and L ₈ have the same meaning as L ₁ . p ₂ has the same meaning as p ₁ . q ₂ has the same meaning as q ₁ . n ₂ has the same meaning as n ₁ . X ₂ has the same meaning as X ₁ , and k ₂ has the same meaning as k ₁ . The compounds represented by formulas (I) to (IV) are described in detail below. R ³ , R ⁴ , R
^The alkyl group represented by ⁵ or R ⁶ may be substituted and is preferably one having 4 or less carbon atoms, particularly preferably a methyl group, an ethyl group, a hydroxyalkyl group or an aminoethyl group. The alkoxy group may be substituted and is preferably one having 4 or less carbon atoms, particularly preferably a methoxy group, an ethoxy group, a methoxyethoxy group or a hydroxyethoxy group. The amino group may be substituted with an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or the like, and the substituents may form a ring, and those having 8 or less carbon atoms are preferable. Particularly preferred is a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a hydroxyethylamino group, a morpholino group, or a pyrrolidino group. Also R
Hydrogen atom linked to the nitrogen atom adjacent to ^one carbonyl group or a sulfonyl group are dissociable, thus R ² by the presence of such a base ^{_{- (CH 2) r -CON -}} SO 2 R
_{^{3, - (CH 2) S}} -SO 2 N - COR 4, - (CH 2) t
-CON ^- COR ⁵ or _{- (CH 2) u -SO 2} N - S
It can take the form of O ₂ R ⁶ . The alkyl group represented by R ² is preferably one having 5 or less carbon atoms, particularly preferably a methyl group, an ethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group,
A carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.
Preferred values of r, s, t, or u are 1,
A few.

The 5- or 6-membered heterocyclic nucleus represented by Z ^{1 to} Z ⁶ is a thiazole nucleus (thiazole nucleus (eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4, 5-diphenylthiazole), a benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole,
5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole,
6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole,
5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6- Methylbenzothiazole, tetrahydroxybenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d]) Thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3]
3-d] thiazole)}, thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole) , 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (eg, benzoxazole, 5-chlorobenzoxazole, 5-
Methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5- Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole,
5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1
-D] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole)}, oxazoline nucleus (eg, 4,4-dimethyloxazoline) ), Selenazole nuclei {selenazole nuclei (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nuclei (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitro) Benzoselenazole, 5-methoxybenzoselenazole,
5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d]) Selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {terrazole nucleus (eg,
Tellurazole, 4-methylterrazole, 4-phenylterrazole), benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-
Methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzoterrazole), naphthoterrazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)} , A tellrazoline nucleus (for example, tellrazoline, 4-methylterrazoline), 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5- Cyanoindolenine, 3,3-dimethyl-6-nitroindolenine,
3,3-dimethyl-5-nitroindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus {imidazole nucleus (for example, 1-alkylimidazole, 1-alkyl-4-
Phenylimidazole, 1-arylimidazole),
Benzimidazole nuclei (for example, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5- Cyanobenzimidazole, 1
-Alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole,
1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzo Imidazole 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5
-Cyanobenzimidazole), a naphthoimidazole nucleus (for example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [2,1-d] imidazole), and the aforementioned alkyl group has 1 to 8 carbon atoms. thing,
For example, methyl, ethyl propyl, isopropyl,
An unsubstituted alkyl group such as butyl or a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl) is preferable. Particularly preferred are methyl group and ethyl group. The aforementioned aryl groups are phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl)
Substituted phenyl represents an alkoxy (eg methoxy) substituent phenyl. }, Pyridine nucleus (for example, 2-pyridine nucleus (for example, 2-pyridine, 4-pyridine), 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {for example, 2-quinoline, 3 -Methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-
Quinoline, 6-nitro-2-quinoline, 8-fluoro-
2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4
-Quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-
Methoxy-4-quinoline, 6-methyl-4-quinoline,
6-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (eg, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-
Nitro-3-isoquinoline)}, imidazo [4,5-
b] quinoxaline nucleus (eg 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-
Diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,
Examples include a pyrimidine nucleus and a pyrroline nucleus.

Among these heterocyclic nuclei, preferred are thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, quinoline nucleus, and pyrroline. Nucleus, thiazoline nucleus,
It is a tetrazole nucleus.

Y ¹ and Y ² represent an atomic group necessary for forming a 5- or 6-membered acidic nucleus. The acidic nucleus referred to herein is, for example, "The Theory of Ed." Edited by James.・ The Photographic Process "(The Th
eory of the Photographic Process) Fourth Edition, Macmillan Publishing Company, 1977, p. 198. Specifically, US Pat. Nos. 3,567,719 and 3,5
75,869, 3,804,634, 3,83
7,862, 4,002,480, 4,92
No. 5,777, and those described in JP-A-3-167546 and the like. The following nuclei are preferable. 2-pyrazolin-5-one, pyrazolidine-
3,5-dione, imidazolin-5-one, hydantoin, 2 or 5-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one, 2
-Thiooxazolidine-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodamine, thiazolidine-2,4-dithione, isorhodanine , Indoline-2-one, indoline-3-one,
Indazolin-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-
6,7-dihydrothiazolo [3,2-a] pyrimidine,
3,4-dihydroisoquinolin-4-one, barbituric acid, 2-thiobarbituric acid, indazoline-2-one, or pyrido [1,2-a] pyrimidin-1,3-
The core of Zeon. Among these nuclei, more preferable ones are rhodanine, hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazolidine-2,4-dione, barbituric acid,
Examples include 2-thiobarbituric acid and 2-pyrazolin-5-one.

The methine group represented by L _{1 to} L ₁₀ may be substituted, and the substituent may be an alkyl group (eg, methyl group, ethyl group, 2-carboxyethyl group) which may be substituted, or may be substituted. Good aryl group (eg phenyl group, o-carboxyphenyl group), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy group, ethoxy group), alkylthio group (eg methylthio group, ethylthio group), etc. And may form a ring with another methine group, or may form a ring with an auxochrome. Specific examples of the compounds represented by formulas (I) to (IV) are shown below, but the scope of the present invention is not limited thereto.

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11]

[0019]

[Chemical 12]

[0020]

[Chemical 13]

[0021]

[Chemical 14]

[0022]

[Chemical 15]

[0023]

[Chemical 16]

[0024]

[Chemical 17]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

[0027]

[Chemical 20]

[0028]

[Chemical 21]

[0029]

[Chemical formula 22]

[0030]

[Chemical formula 23]

[0031]

[Chemical formula 24]

[0032]

[Chemical 25]

[0033]

[Chemical formula 26]

[0034]

[Chemical 27]

[0035]

[Chemical 28]

[0036]

[Chemical 29]

[0037]

[Chemical 30]

[0038]

[Chemical 31]

[0039]

[Chemical 32]

[0040]

[Chemical 33]

[0041]

[Chemical 34]

[0042]

[Chemical 35]

[0043]

[Chemical 36]

The methine compounds represented by the general formulas (I) to (IV) can be synthesized according to the method shown below.

The compounds represented by the general formulas (I) to (IV) according to the present invention are known as "Heterocyclic Compounds-Cyanine Soybean and Reelated Compounds" by FM Hamer.
ic Compounds-Cyanine Dyes and Related Compounds
(John Wiley & Sons
N.S.-New York, London, 1964, DM Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry" (Heterocycl
ic Compounds-Special topics in heterocyclic chemi
stry-) ", Chapter 18, Section 14, 482-515
Page, John Wiley and Sons
& Sons) -New York, London, (1977). , "Rodd's Chemistry of Carbon Compound
s) ”, (2nd. Ed. vol.IV, part B, published in 1977), Chapter 15, pp. 369-422; (2nd. Ed. vo
l. IV, part B, 1985), Chapter 15, 267
~ 296, Elsvier Science Publishing C
ompany Inc.), New York. It can be synthesized based on the method described in.

General formulas (I) to (IV) used in the present invention
The compound represented by can be directly dispersed in the emulsion, or can be dissolved in a suitable solvent (eg, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof and added to the emulsion. it can. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. Further, it can be dispersed and added to the emulsion by the method described in JP-A-50-80119.

The silver halide used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. Gives a silver halide emulsion having a substantially uniform grain size. When forming the silver halide grains used in the present invention, as a silver halide solvent for controlling the growth of the grains, for example, ammonia, rhodancali, rhodanammon, thioether compounds (for example, US Pat. Nos. 3,271,157 and 3). , 574,628, 3,704,130, 4,297,439, 4,276,374, etc.), thione compounds (for example, JP-A-53-144,31).
No. 9, No. 53-82, 408, No. 55-77, 7
37), amine compounds (for example, JP-A-54-10).
No. 0,717, etc.) can be used. The average grain size of silver halide is preferably 1.0 μm or less, and particularly preferably 0.7 μm or less. See CE Mees and TH James for details on how to determine average particle size.
Written by: The Theory of the Photoglaphic Process, 3
rd ed. P. 36-P. 43, (1966, McMillan
You can refer to the magazine.

The silver halide grains used in the present invention have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles may also be large-sized particles having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion that can be used in the present invention is
For example, Research Disclosure (RD) No. 1
7643 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", ibid.
8716 (November 1979), p.648, ibid., No. 30.
7105 (Nov. 1989), pages 863-865, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides.Chemie et Phisique Photographique, P.
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photograph
ic Emulsion Chemistry, Focal Press, 1966) and "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al., Making and Coat).
ing Photographic Emulsion, Focal Press, 1964)
And the like.
U.S. Pat. Nos. 3,574,628 and 3,655,39
Monodisperse emulsions described in, for example, No. 4 and British Patent No. 1,413,748 are also preferable. Also, the aspect ratio (A
AgX with gX particles having a circle equivalent diameter / particle thickness of about 3 or more
An emulsion in which grains are present in an amount of 50% (area) or more of all AgX grains in the emulsion can also be used in the present invention. Tabular grains are described by Gaft, Gutoff, Photographic Science and Engin.
eering), Vol. 14, pp. 248-257 (1970),
U.S. Pat. Nos. 4,434,226 and 4,414,31
0, 4,433,048, 4,439,520
No. 2,112,157 and the like, and can be easily prepared.

In the present invention, it is preferable to use a water-soluble rhodium salt, typically rhodium chloride, rhodium trichloride, rhodium ammonium chloride and the like. Furthermore, these complex salts can also be used. The addition time of the rhodium salt is limited before the completion of the first ripening during emulsion production, and it is particularly preferable to add it during grain formation. The addition amount is 1 × 10 ^-8 mol or more per 1 mol of silver, 1 × The range of 10 ^-6 mol or less is preferable. Further, a water-soluble iridium salt such as Na ₃ IrCl ₆ : Na ₂ IrCl ₆ can be used. The water-soluble iridium salt is preferably added before the first ripening during the production of the emulsion, particularly during grain formation. The addition amount is preferably in the range of 1 × 10 ⁻⁸ mol or more and 1 × 10 ⁻⁵ mol or less.

The gold sensitizer used in the present invention includes various gold salts such as potassium chloroaurite, potassium auric thiocyanate, potassium chloroaurate and auric trichloride. Specific examples are described in US Pat. Nos. 2,399,083 and 2,642,361. As the sulfur sensitizer used in the present invention, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. Specific examples are U.S. Pat. Nos. 1,574,944 and 2,278,947.
No. 2, ibid. 2,410,689, ibid. 2,728,668
Nos. 3,501,313 and 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds. The preferable addition amounts of the sulfur sensitizer and the gold sensitizer are 10 ^-2 to 10 per mol of silver.
^-7 mol, more preferably 1 x 10 ^{-3 to} 5 x 10 ^-6 mol. The molar ratio of sulfur sensitizer to gold sensitizer is 1 :.
It is 3 to 3: 1 and preferably 1: 2 to 2: 1. In the present invention, a reduction sensitization method can be used. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used. The temperature for carrying out the chemical sensitization of the present invention is from 30 ° C. to 9
It can be selected from any temperature between 0 ° C. Further, the pH during chemical sensitization is 4.5 to 8.5, preferably 5.0 to 7.0. The time of chemical sensitization cannot be decided because it varies depending on the temperature, amount of chemical sensitizer used, pH, etc., but it can be arbitrarily selected from a few minutes to a few hours, and usually 10 minutes to 200 minutes. Done.

Infrared spectral sensitization of a silver halide emulsion sometimes deteriorates the stability of the emulsion in solution.
In order to prevent this, it is effective to add a water-soluble bromide to the emulsion. As the water-soluble bromide, various compounds capable of dissociating into bromide ions in water can be used. For example, salts of bromides such as ammonium, potassium, sodium, lithium and the like can be used. Also, a suitable organic bromide, such as tetraethylammonium bromide, ethyl pyridinium bromide, etc., can be used. However, of the bromide salts, cadmium bromide, zinc bromide and the like are toxic when they are excessively absorbed by the human body, and thus the harmless water-soluble bromide described above is preferable. The amount of water-soluble bromide added to the emulsion is sufficient to substantially increase the sensitivity of the emulsion and / or substantially eliminate sensitivity changes over time.
The amount of water-soluble bromide can be varied over a wide range, but particularly good results have been obtained with 0.0003 to 0.
It can be obtained when added in the range of 01 mol.
Even better results are that bromide is 0.0005 per mole of silver.
Obtained when added in the range of 0.005 mol.
The amount of the bromide is the amount added to the anion of the sensitizing dye when the anion of the sensitizing dye is bromine or bromide. The water-soluble bromide may be added at any time after the formation of silver halide grains, but it is preferably after the completion of chemical sensitization.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Pat. Nos. 3,703,377, 2,688,545, 3,397,060, 3,615,635,
No. 3,628,964, British Patent Nos. 1,242,5.
No. 88, No. 1,293,862, Japanese Patent Publication No. 43-49
No. 36, No. 44-14030, No. 43-10773
No. 3, U.S. Pat. No. 3,416,927, Japanese Patent Publication No. 43-4
930, U.S. Pat. Nos. 3,615,613 and 3,
The sensitizing dyes described in No. 615,632, No. 3,617,295, No. 3,635,721 and the like can be used.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. Those compounds are nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,
3,3a, 7-tetraazaindene, 1-phenyl-5
-Many heterocyclic compounds including mercaptotetrazole, mercury-containing compounds, mercapto compounds, and extremely many compounds such as metal salts have been known for a long time. An example of a compound that can be used is "The Theory of the Phot" by K. Mees.
Other compounds described in the original document on pages 344 to 349 of "Graphic Process" (3rd edition, 1966) include, for example, U.S. Pat. Nos. 2,131,038 and 2,694,716. Thiazolium salts described in US Pat. Nos. 2,886,437 and 2,44.
Azaindenes described in U.S. Pat. No. 4,605; urasols described in U.S. Pat. No. 3,287,135; sulfocatechols described in U.S. Pat. No. 3,236,652; British Patent No. 623
Oximes described in U.S. Pat. No. 448; mercaptotetrazoles described in U.S. Pat. Nos. 2,403,927, 3,266,897 and 3,397,987, nitrones; Nitroindazoles;
Polyvalent metal salts described in U.S. Pat. No. 2,839,405; thiuronium salts described in U.S. Pat. No. 3,220,839; U.S. Pat. 2,566,2
No. 63, No. 2,597,915 and the like, and salts of palladium, platinum and gold.

Silver halide photographic emulsions include developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines, or a combination of developing agents. Can be included. Developing agents can be incorporated in the silver halide emulsion layers and / or other photographic layers (eg protective layers, interlayers, filter layers, antihalation layers, back layers, etc.). The developing agent is dissolved in a suitable solvent, or US Pat. No. 2,59
It can be added in the form of the dispersions described in 2,368 and French Patent 1,505,778.

Examples of development accelerators include US Pat. Nos. 3,288,612, 3,333,959, 3,345,175, and 3,708,303.
British Patent No. 1,098,748, West German Patent No. 1,
The compounds described in Nos. 141, 531 and 1,183,784 can be used.

The photographic emulsion of the present invention may contain an inorganic or organic hardener. For example, chrome salt (chrome alum,
Chromium acetate, etc., aldehydes (formaldehyde,
Glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-
Dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid etc.) isoxazoles, dialdehyde starch, 2
-Chlor-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Specific examples thereof include U.S. Pat. Nos. 1,870,354 and 2,080,
No. 019, No. 2,726,162, No. 2,870,0
No. 13, No. 2,983,611, No. 2,992,10
No. 9, No. 3,047,394, No. 3,057,723
No. 3,103,437, No. 3,321,313
Issue 3, Issue 3,325,287, Issue 3,362,827
No. 3,539,644, No. 3,543,292
No., British Patents 676,628, 824,544,
1,270,578, German Patent 872,153
No. 1,090,427, JP-B-34-7,133
No. 46-1872 and the like.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material prepared by using the present invention may be coated with an auxiliary agent such as coating aid, antistatic agent, improving slip property, emulsifying dispersion, preventing adhesion and improving photographic characteristics (for example, development acceleration). , Hardening, sensitization)
Various surfactants may be included. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters,
Polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Nonionic surfactants such as glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid Salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants containing an acidic group such as carboxy group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group such as esters; amino acids, aminoalkyl sulfonic acids, amino Amphoteric surfactants such as alkyl sulfates or phosphates, alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium , And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

For the purpose of improving the sharpness of the legs of the characteristic curve and obtaining high-quality halftone dots and line images, etc., polyalkylene oxide compounds (for example, alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide and propylene). −
1,2-oxide, butylene-1,2-oxide and the like, preferably polyalkylene oxide consisting of at least 10 units of ethylene oxide, and water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, hexitol derivative and the like. A condensate with a compound having at least one active hydrogen atom or a block copolymer of two or more kinds of polyalkylene oxides) can be used. Specific examples of compounds include JP-A-50-156.
423, JP-A-52-108130, and JP-A-5-108130.
The polyalkylene oxide compound described in No. 3-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

As the binder or protective colloid of the photographic emulsion, 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, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric substances such as polyvinylpyrazole and other single or copolymers can be used.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. As the gelatin derivative, gelatin is reacted with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds. What is obtained is used.
Specific examples thereof are US Pat. Nos. 2,614,928 and 3,1.
32,945, 3,186,846, 3,31
2,553, British Patents 861,414, 1,03
No. 3,189, No. 1,005,784, Japanese Patent Publication No. 42-
No. 26845. The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate A polymer having a monomer component of a combination of styrene, sulfoalkyl (meth) acrylate, and styrenesulfonic acid can be used. Also, various additives can be used depending on the purpose. Although the above-mentioned various additives are used in the light-sensitive material of the present invention, various additives other than the above can be used depending on the purpose. These additives are described in more detail in Research Disclosure Item 1764
3 (December 1978) and Item 18716 (1)
(November 979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 1 Chemical sensitizer page 648, right column 2 Sensitivity enhancer same as above 3 Spectral sensitizer, supersensitizer 23 to 24 pages 648 right column to 649 right column 4 Whitening agent 24 pages 5 Antifoggant, and safety page 24 to 25, page 649, right column, fixed agent 6 Light absorber, filter dye, page 25 to 26, page 649, right column to page 650, left column, UV absorber, 7 stain inhibitor, page 25, right column Page 650 Left to right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Page left column 10 Hinder 26 page Ibid. 11 Plasticizer, lubricant page 27 650 page right column 12 Coating aid, surface active agent 26 Page 27, page 650, right column 13 antistatic agent, page 27 Same as above Various color couplers can be used in the invention, and specific examples thereof include Research Dixloger (RD) No. 17643, VII-mentioned above. It is described in the patents described in C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,022.
No. 620, No. 4,326,024, No. 4,40
Nos. 1,752, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760 are preferred. 5 for magenta coupler
-Pyrazolone-based and pyrazoloazole-based compounds are preferable, and U.S. Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June, 2013), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, and U.S. Pat. No. 4,500,63.
Those described in No. 0, No. 4,540, 654 and the like are particularly preferable. Examples of cyan couplers include phenol-type and naphthol-type couplers, and for example, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296. No. 200,
No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
173, West German Patent Publication 3,329,729, European Patent 121,365A, US Patent 3,446,6.
No. 22, No. 4,333, 999, No. 4,451,
No. 559, No. 4,427,767, European Patent No. 16
Those described in No. 1,626A are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G,
U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-394
13, U.S. Pat. Nos. 4,004,929 and 4,1.
Those described in 38,258 and British Patent 1,146,368 are preferable. Examples of the coupler in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237,
British Patent No. 2,125,570, European Patent No. 96,5
70 and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers include U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and British Patent 2,102,173. It is described in. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD1764, VII above.
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Those described in U.S. Pat. No. 4,248,962 are preferred. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
No. 185950, JP-A No. 62-24252, DIR redox compound or DIR coupler-releasing coupler or DIR coupler-releasing coupler or redox, and dye releasing after recovery described in EP 173,302A. Coupler, R.E. D. No. 114
No. 49, No. 24241, and the bleaching accelerator releasing coupler described in JP-A No. 61-201247, U.S. Pat.
Examples thereof include ligand releasing couplers described in 3,477 and the like.

Any photographic developing method may be applied to the light-sensitive material of the present invention. Examples of the developing agent used in the developing solution include a dihydroxybenzene-based developing agent, a 1-phenyl-3-pyrazolidone-based developing agent, a p-aminophenol-based developing agent, a p-phenylenediamine-based developing agent, and the like, either alone or in combination. (For example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes or p
-Aminophenols and dihydroxybenzenes) can be used. Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone. In the above, examples of the dihydroxybenzene type developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, tolhydrohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, and 2,5-dimethylhydroquinone, and 1-phenyl. As the 3--3-pyrazolidone developing agent, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4, 4-dihydroxymethyl-1-phenyl-3-pyrazolidone and the like, and p-aminophenol-based developing agents such as p-aminophenol and N-methyl-p-aminophenol are used. As a developing agent for color photographic light-sensitive materials, p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-.
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and sulfates thereof,
Hydrochloride or p-toluene sulfonic acid salt etc. are mentioned. Two or more of these compounds can be used in combination depending on the purpose. A compound that gives free sulfite ion, such as sodium sulfite, potassium sulfite, potassium metabisulfite, or sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, formaldehyde sodium bisulfite which gives almost no free sulfite ion in the developer may be used. As the alkaline agent of the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate,
Tribasic potassium phosphate, diethanolamine, triethanolamine and the like are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developing solution may contain an organic compound known as an antifoggant or a development control agent. Examples thereof include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example Triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazain Such as down like; benzenethiosulfonate, benzene sulfinic acid, benzenesulfonic acid amide, 2
-Mercaptobenzimidazole-5-sodium sulfonate and the like. The developer which can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, molecular weight 1000 to 10
0.1 to 10 g of polyethylene oxide, etc.
It can be contained in the range of / liter. It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, diethylenetetraaminepentaacetic acid and the like as a water softening agent to the developer which can be used in the present invention.

As the fixing liquid, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The fixing solution may contain a complex of ethylenediaminetetraacetic acid and a trivalent iron ion as a sulfiding agent.

The processing temperature and the processing time are appropriately set, but a processing temperature of 18 ° C. to 50 ° C. is usually suitable, while a rapid processing of 15 to 120 seconds using a so-called automatic processor is preferable. Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[0065]

EXAMPLE An emulsion was prepared by the following method. 0.5
M silver nitrate aqueous solution, 0.1M potassium bromide and 0.4
4M sodium chloride, hexachloroiridium (III)
Aqueous halogen salt solution containing potassium acid salt and ammonium hexabromorhodium (III) was added with sodium chloride, 1,3
-Adding to a gelatin aqueous solution containing dimethylimidazolidine-2-thione and benzenethiosulfonic acid adjusted to pH 4.0 by stirring with a double jet method at 38 ° C for 10 minutes, the average particle size was 0.16 µm, and silver chloride was added. Nucleation was performed by obtaining silver chlorobromide grains having a content of 70 mol%. Then, similarly, 0.5M silver nitrate aqueous solution,
A halogen salt aqueous solution containing 0.1 M potassium bromide, 0.44 M sodium chloride and potassium ferrocyanide was added by the double jet method for 10 minutes to complete the grain formation. The obtained particles have an average particle size of 0.2 μm, a silver chloride content of 70 mol%, and an Ir of 3.8 × 1 per mol of silver.
0 ^-7 mol, Rh 6.1 x 10 ^-8 mol, Fe 2.3 x
It was a silver chlorobromide cubic grain containing 10 ⁻⁵ mol (variation coefficient: 10%). Then, it was washed with water by a flocculation method according to a conventional method and 30 g of gelatin was added.

The pH of this emulsion was 5.6 and pAg was 7.5.
Adjusted to 6.0 m of sodium thiosulfate per mol of silver.
g, 8.0 mg of chloroauric acid was added, and chemical sensitization treatment was performed at 65 ° C. so as to obtain optimum sensitivity, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrayl was used as a stabilizer. The indene 75 mg was added.

Each dye was added to the resulting emulsion as shown in Table 1. Further, 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbenedisulphonic acid disodium salt was added at 234 mg per mol of silver, 1-
25 mg of phenyl-5-mercaptotetrazole was added. Furthermore, hydroquinone 150 mg / m ² and polyethyl acrylate latex were used in a gelatin binder ratio of 30%,
Colloidal silica of 0.01 μm was added with a gelatin binder ratio of 30%, and 2-bis (vinylsulfonylacetamide) ethane was added as a hardening agent in an amount of 70 mg / m ² , and a silver coating amount was 3.2 g / m ² on a polyester support. The amount of gelatin coated was 1.4 g / m ² . At this time, 0.5 g / m ^{2 of} gelatin was added to the upper layer of the emulsion layer as a protective layer, 70 mg / m ² of a dye having the following structural formula, and a matting agent with a particle size of 2.5
60 mg / m ^{2 of} polymethylmethacrylate of μm, particle size 1
Colloidal silica 70 mg / m ² of 0 .mu.m, also the fluorine-containing surfactant 1.5 mg / m ² and chelating agent 20 mg / m ² of sodium dodecylbenzenesulfonate and the following structural formula was added as a coating aid, pH 5. It was adjusted to 5 and coated simultaneously with the emulsion layer.

[0068]

[Chemical 37]

[0069]

[Table 1]

The base used in this example has a back layer and a back protective layer having the following compositions. (Back layer) Gelatin 2.0 g / m ² Sodium dodecylbenzene sulfonate 80 mg / m ²

[0071]

[Chemical 38]

1,3-divinylsulfone-2-propanol 60 mg / m ² (back protective layer) gelatin 0.5 g / m ² polymethyl methacrylate (particle size 4.7 μm) 30 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² Fluorine-containing surfactant (above) 2 mg / m ² Silicone oil 100 mg / m ²

Evaluation of Photographic Performance The obtained sample was exposed to xenon flash light with an emission time of 10 ⁻⁵ seconds through an interference filter having a peak at 515 nm and a continuous wedge, and was then developed by Fuji Photo Film Co., Ltd. Sensitometry was performed using FG-710NH at the temperature and time shown below.

Development 38 ° C. 14 sec Fixing 37 ° C. 9.7 sec Washing 26 ° C. 9 sec Squeeze 2.4 sec Dry 55 ° C. 8.3 sec Total 43.4 sec Linear velocity 2800 mm / min , Has the following composition. (Developer formulation) Potassium hydroxide 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.6 g Potassium bromide 3.3 g 5-Methylbenzotriazole 0.08 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 0. 3 g Potassium sulfite 83 g Hydroquinone 35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.3 g Diethylene glycol 30 g Water was added to 1 liter (sodium hydroxide was added to adjust pH = 10.7) (fixing) Liquid formulation) ammonium thiosulfate 150 g 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate 0.25 mol sodium bisulfite 30 g ethylenediaminetetraacetic acid disodium dihydrate 0.025 g water 1 liter (water Adjustment with sodium oxide to pH = 6.0) Evaluation of sensitivity and gradation The relative sensitivity was evaluated using the logarithm of the exposure amount giving a density of 3.0 as the sensitivity. Evaluation of residual color The unexposed sample was processed in the same manner as the evaluation of sensitivity except that the washing water temperature was set to 5 ° C., and the tint of the sample was visually evaluated in five levels. 5 means the least residual color, 1 means the most residual color, and 3 means the practical limit. The evaluation results of each sample are shown in Table 2.

[0075]

[Table 2]

As is clear from Table 2, it is understood that Sample Nos. 5, 6, and 7 which correspond to the present invention are excellent in sensitivity and residual color.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 11, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[0018]

[Chemical 11]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

[0028]

[Chemical 21]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

[Chemical 31]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

[Chemical 35]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

The compounds represented by the general formulas (I) to (IV) according to the present invention are known as "Heterocyclic Compounds-Cyanine Soybean and Reelated Compounds" by FM Hamer.
ic Compounds-Cyanine Dyes and Related Compounds
(John Wiley & Sons
N.S.-New York, London, 1964, DM Sturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry" (Heterocycl
ic Compounds-Special topics in heterocyclic chemi
stry-) ", Chapter 18, Section 14, 482-515
Page, John Wiley and Sons
& Sons) -New York, London, (1977). , "Rodd's Chemistry of Carbon Compound
s) ”, (2nd. Ed. vol.IV, part B, published in 1977), Chapter 15, pp. 369-422; (2nd. Ed. vo
l. IV, part B, 1985), Chapter 15, 267
~ 296 pages, Elsevier Science Publishing Company, Inc.
ing Company Inc.), New York. It can be synthesized based on the method described in.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

General formulas (I) to (IV) used in the present invention
The compound represented by can be directly dispersed in the emulsion, or can be dissolved in a suitable solvent (eg, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof and added to the emulsion. it can. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. Further, the dispersion is added to the emulsion by the method described in JP-A-50-80119, or mechanically ground and dispersed in a hydrogen solvent by the method described in JP-B-61-45217, and the dispersion is obtained. Can also be added to the emulsion.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Infrared spectral sensitization of a silver halide emulsion sometimes deteriorates the stability of the emulsion in solution.
In order to prevent this, it is effective to add a water-soluble bromide to the emulsion. As the water-soluble bromide, various compounds capable of dissociating into bromide ions in water can be used. For example, salts of bromides such as ammonium, potassium, sodium, lithium and the like can be used. Also, a suitable organic bromide such as tetraethyl ammonium bromide or ethyl pyridinium bromide may be used. However, of the bromide salts, cadmium bromide, zinc bromide and the like are toxic when they are excessively absorbed by the human body, and thus the harmless water-soluble bromide described above is preferable. The amount of water-soluble bromide added to the emulsion is sufficient to substantially increase the sensitivity of the emulsion and / or substantially eliminate sensitivity changes over time.
The amount of water-soluble bromide can be varied over a wide range, but particularly good results have been obtained with 0.0003 to 0.
It can be obtained when added in the range of 01 mol.
Even better results are that bromide is 0.0005 per mole of silver.
Obtained when added in the range of 0.005 mol.
The amount of the bromide is the amount added to the anion of the sensitizing dye when the anion of the sensitizing dye is bromine or bromide. The water-soluble bromide may be added at any time after the formation of silver halide grains, but it is preferably after the completion of chemical sensitization.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

Development 38 ° C. 14 sec Fixing 37 ° C. 9.7 sec Washing 26 ° C. 9 sec Squeeze 2.4 sec Dry 55 ° C. 8.3 sec Total 43.4 sec Linear velocity 2800 mm / min , Has the following composition. (Developer formulation) Potassium hydroxide 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.6 g Potassium bromide 3.3 g 5-Methylbenzotriazole 0.08 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 0. 3 g Potassium sulfite 83 g Hydroquinone 35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.3 g Diethylene glycol 30 g Water was added to 1 liter (sodium hydroxide was added to adjust pH = 10.7) (fixing) Liquid formulation) ammonium thiosulfate 150 g 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate 0.25 mol sodium bisulfite 30 g ethylenediaminetetraacetic acid disodium dihydrate 0.025 g water 1 liter (water Adjustment to pH = 6.0 with sodium oxide) Evaluation of sensitivity The sensitivity was evaluated by the relative sensitivity with the logarithm of the exposure amount giving a concentration of 3.0 being taken as the sensitivity. Evaluation of residual color The unexposed sample was processed in the same manner as the evaluation of sensitivity except that the washing water temperature was set to 5 ° C., and the tint of the sample was visually evaluated in five levels. 5 means the least residual color, 1 means the most residual color, and 3 means the practical limit. The evaluation results of each sample are shown in Table 2.

Claims (2)

[Claims] 1. A halogen containing at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II) or general formula (IV). Silver halide photographic light-sensitive material. General formula (I) In the formula, R ¹ _{- (CH 2) r -CONHSO 2} -R 3, -
_{(CH 2) s -SO 2 NHCO} -R 4, - (CH 2) t -C
ONHCO-R ⁵ _{or, - (CH 2) u -SO} 2 NHS
Representing the O ₂ -R ^6. Here, R ³ , R ⁴ , R ⁵ , or R ⁶ represents an alkyl group, an alkoxy group, or an amino group, and r, s, t, or u represents an integer of 1 to 5. R ² represents a different alkyl group of whether synonymous with R ¹ or R ^1,. Z ¹ and Z ² may be the same or different and each represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle. L ₁ , L ₂ or L ₃ represents a methine group, and n ₁ represents 0, 1 or 2. X ₁
Represents an anion, and k ₁ represents a number necessary for adjusting the charge in the molecule to zero. p ₁ or q ₁ is 0 or 1
Represents General formula (II) In the formula, Z ³ represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. Y ¹ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered acidic nucleus. R ⁷ and R ⁸ represent alkyl groups other than those defined for R ¹ . v ₁ represents 0 or 1. w ₁ represents 0, ₁ , 2 or 3. L ₄ and L ₅ have the same meaning as L ₁ . General formula (IV): In the formula, Z ⁶ has the same meaning as Z ³ , and Y ² has the same meaning as Y ¹ . R ¹¹ or R ¹² represents an alkyl group, but at least one of them represents a substituent defined by R ¹ . L ₉ and L ₁₀ have the same meaning as L ₁ . v ₂ is synonymous with v ₁ and w ₂ is w
Synonymous with ₁ . 2. A halogenation comprising at least one compound represented by the following general formula (III) and at least one compound represented by the general formula (IV) according to claim 1. Silver photographic light-sensitive material. General formula (III): In the formula, Z ⁴ and Z ⁵ have the same meaning as Z ¹ . R ⁹ and R ¹⁰ represent alkyl groups other than those defined for R ¹ . L
₆ , L ₇ and L ₈ have the same meaning as L ₁ . p ₂ is p ₁
Is synonymous with. q ₂ has the same meaning as q ₁ . n ₂ has the same meaning as n ₁ . X ₂ has the same meaning as X ₁ , and k ₂ has the same meaning as k ₁ .