JPH09152675A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the spectral sensitivity of a wavelength region from green to red and to ameliorate a staining property with after-colors by incorporating silver halide particles spectrally sensitized with specific compds. into silver halide emulsion layers. SOLUTION: The silver halide particles spectrally sensitized with the compd. expressed by formula are incorporated into at least one layer of the silver halide emulsion layers. In the formula, Y denotes a (substd.) imino group, oxygen atom, sulfur atom, selenium atom or tellurium atom which may have a substituent, Q denotes the atom group necessary for perfection of a 5- or 6-membered nitrogenous heterocycle (this nitrogenous heterocycle has a substituent); R<1> denotes <=10C aliphat. group substd. for a water solubilizing group; n denotes 0 or 1; R<2> denotes an aralkyl group when n=0 and R<2> denotes an alkyl group, alkyl group or aralkyl group when n=1. V<1> , V<2> denote hydrogen atoms, alkyl group, alkoxy groups, etc. V<1> and V<2> may bond to form a condensed ring which may have a substituent.

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, and more particularly to a silver halide photographic light-sensitive material (hereinafter, referred to as "a silver halide photographic light-sensitive material" having improved spectral sensitivity in a wavelength range from green to red and improved residual color contamination. "Photosensitive material").

[0002]

2. Description of the Related Art A silver halide emulsion (hereinafter referred to simply as "emulsion")
(Also referred to as)) is known as a spectral sensitization technique, and a spectral sensitizing dye used for this purpose is known to be a large number of compounds such as cyanine dyes and merocyanine dyes. Has been.

These spectral sensitizing dyes (hereinafter, also referred to as "sensitizing dyes" or simply "dyes") must not only expand the light-sensitive wavelength region of the emulsion, but also satisfy the following conditions. I have to.

1) Appropriate spectral sensitization range 2) High spectral sensitization efficiency 3) Do not adversely affect the characteristic curve such as fog generation and gamma change 4) Photosensitizing dye containing sensitizing dye Do not change the photographic performance such as fog when the material is aged (especially when it is stored under high temperature and high humidity) 5) The added sensitizing dye diffuses into the layers of different photosensitized wavelength range to cause color turbidity. 6) After developing, fixing and washing with water, the sensitizing dye disappears,
Do not cause color pollution.

However, the conventionally disclosed spectral sensitizing dyes have not yet reached the level of satisfying all of these various conditions. In particular, the development processing time is shortened,
With the introduction of anhydrous washing and recycling of the treatment liquid, the dye tends to remain. as a result,
Color contamination (hereinafter referred to as "residual color contamination") appears in the processed light-sensitive material, which causes a problem of remarkably reducing commercial value. That is, improvement of residual color contamination in the sensitizing dye has become an important technical issue.

Examples of sensitizing dyes for spectrally sensitizing the green light wavelength region include, for example, US Pat. Nos. 2,072,908 and 2,6.
47,053, British Patent 1,012,825 and the like, oxacarbocyanine dyes, JP-B-38-78
No. 28, No. 43-14497, No. 44-14030
No. 51/31228, British Patent 815,17
2, U.S. Pat. Nos. 2,778,823 and 2,739,
149, 2,912,329, 3,656,9
Benzimidazolocarbocyanine dyes described in US Pat. No. 59, etc., oxathiacarbocyanines described in British Patent 1,012,825, or US Pat.
No. 8, No. 2,519,001, No. 3,480,439
No. european patent 435,136, JP-A-46-1630
No. 49-134315, No. 51-140622.
No. 54-61519, No. 55-45015, No. 61-118743, and the like are known.

Further, as a sensitizing dye for spectrally sensitizing a red light wavelength region, for example, Belgian Patent No. 541,245, US Patent Nos. 2,493,747 and 2,493,748 are cited.
Nos. 2,743,272 and 3,335,010
French patent 2,113,248 German patent 1,02
4,800, 2,153,570, 2,30
No. 0,321, complex cyanine dyes and complex merocyanine dyes described in JP-A-3-171135 and the like, JP-A-49-11121 and JP-A-51-3362.
No. 2, No. 51-115821, No. 51-115822
No. 58-72937, No. 61-203446,
Cyanine dyes described in JP-A-2-256045 and JP-A-3-15042, U.S. Pat. Nos. 2,493,747, 2,493,748, 2,519,001, and JP-A-51-106422. No. 59-214030 and the like are known to be effective.

When these dyes are used alone, the ultimate maximum sensitivity is generally low, and some of them give high green light sensitivity or red light sensitivity, but there is a drawback that residual color contamination is significantly deteriorated. Therefore, there has been a strong demand for a technique which satisfies both high sensitivity and low residual color contamination by using a sensitizing dye alone.

[0009]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material having improved spectral sensitivity in the green to red wavelength region and improved residual color contamination. .

[0010]

The above object of the present invention is to provide at least one silver halide emulsion layer represented by the following general formula [D
-I] to achieve a silver halide photographic light-sensitive material containing silver halide grains spectrally sensitized.

[0011]

Embedded image

In the formula, Y represents an imino group which may have a substituent, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, and Q represents an atomic group which completes a 5- or 6-membered nitrogen-containing heterocycle. And the nitrogen-containing heterocycle has a substituent. R ¹ represents an aliphatic group having 10 or less carbon atoms substituted with a water-solubilizing group,
n represents 0 or 1. When n = 0, R ² represents an aralkyl group, and when n = 1, R ² represents an alkyl group, an aryl group or an aralkyl group. V ¹ and V ² are each a hydrogen atom,
It represents an alkyl group, an alkoxy group or an aryl group. In addition, V ¹ and V ² may be bonded to each other to form a condensed ring which may have a substituent.

In particular, the silver halide grains contain 1 × 10 ^-8 to 1 × 10 ^-4 mol of the iridium compound per mol of silver and contain at least 50 mol% of silver chloride. Or a silver halide grain chemically sensitized with at least one selected from a selenium compound and a tellurium compound, the effect is remarkable.

It is disclosed in many patents that the dye stain that remains after processing after dyeing is reduced by substituting a water solubilizing group for part of the dye structure. However, in the case of sensitizing dyes, dyes substituted with a water-solubilizing group are often accompanied by a decrease in the original spectral sensitizing performance, and the types and number of groups to be substituted are limited. By the way, regarding the compound of the present invention having a substituent on the methine chain, there are no examples of disclosure of a specific structure in various documents including patents, and a residue obtained by introducing a group other than a hydrogen atom into the methine chain Neither the effect of reducing color contamination nor the effect of improving spectral sensitization is known. Although the reason why the compound of the present invention reduces the residual color contamination is not clear, introduction of a group other than a hydrogen atom into the methine chain accelerates the hydrolyzability, and decomposition of a part of the structure occurs during the development processing, resulting in decolorization. It is presumed to be due to this.

Hereinafter, the present invention will be described specifically. First,
The compound represented by the general formula [DI] will be described in detail.

In the general formula [DI], the imino group represented by Y is -NH-, which is a branched or straight-chain alkyl group having 1 to 6 carbon atoms (methyl, ethyl, propyl, pentyl, i. -Butyl etc.).

Examples of the aralkyl group represented by R ² include benzyl and phenethyl groups.

The aralkyl group represented by R ² is composed of an alkylene group and an aryl group. Examples of the alkylene group include branched or linear alkylene groups having 1 to 6 carbon atoms (methylene, ethylene, propylene, pentylene, isobutylene, etc.). The aryl group may have a substituent at any position, and examples thereof include phenyl, p-tolyl and 1-naphthyl groups.

The above-mentioned substituent represented by R ² may have a substituent at any position, and as the substituent, a halogen atom (fluorine, chlorine, bromine, iodine atom), a trifluoromethyl group, Alkoxy group (unsubstituted alkoxy group such as methoxy, ethoxy, butoxy, substituted alkoxy group such as 2-methoxyethoxy, benzyloxy), hydroxyl group, cyano group, aryloxy group (phenoxy, tolyloxy, etc.), aryl group (phenyl, p-chlorophenyl etc.), styryl group, heterocyclic group (furyl, thienyl etc.),
Carbamoyl group (carbamoyl, N-ethylcarbamoyl, etc.), sulfamoyl group (sulfamoyl, N, N-
Dimethylsulfamoyl etc.), acylamino group (acetylamino, propionylamino, benzoylamino etc.), acyl group (acetyl, benzoyl etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl etc.), sulfonamide group (methanesulfonylamide, Examples thereof include benzenesulfonamide, etc.), sulfonyl group (methanesulfonyl, p-toluenesulfonyl, etc.), and carboxyl group.

When n = 1, R ² may be an alkyl group or an alkoxy group. As the alkyl group represented by R ² ,
A branched or straight-chain alkyl group having 1 to 6 carbon atoms (methyl, ethyl, propyl, pentyl, i-butyl, etc.)
In addition, examples of the alkoxy group include methoxy and ethoxy.

The aliphatic group represented by R ¹ is, for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (methyl, ethyl, propyl, pentyl, i-butyl, etc.), 3 to 10 atoms. Alkenyl groups (3-butenyl, 2-propenyl, etc.) are mentioned.

R ¹ is an alkoxy group (methoxy, ethoxy, etc.), an aryloxy group (phenoxy, p-tolyloxy, etc.), a cyano group, a carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group). Etc.), sulfamoyl group (sulfamoyl, N, N-3-oxapentamethyleneaminosulfonyl group etc.), methanesulfonyl group, alkoxycarbonyl group (ethoxycarbonyl, butoxycarbonyl etc.), aryl group (phenyl, carboxyphenyl etc.), acyl It may be substituted with a substituent such as a group (acetyl group, benzoyl, etc.).

Examples of the water-solubilizing group substituting for R ¹ include acid groups such as sulfo group, carboxyl group, phosphono group, sulfate group and sulfino group, and carbonylaminocarbonyl group (methanecarbonylaminocarbonyl, trifluoromethyl). Carbonylaminocarbonyl etc.), sulfonylaminocarbonyl group (methanesulfonylaminocarbonyl etc.), carbonylaminosulfonyl group (methanecarbonylaminosulfonyl etc.), sulfonylaminosulfonyl group (methanesulfonylaminosulfonyl etc.) and the like. To be

Specific examples of the aliphatic group substituted with the water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl and ω-sulfopropoxy. Quicarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, There are various groups such as p-carboxybenzyl and methanesulfonylaminocarbonylmethyl.

The alkyl group represented by V ¹ and V ² is a linear or branched alkyl group (methyl, ethyl, i-
Propyl, t-butyl, i-butyl, t-pentyl, hexyl and the like). Examples of the alkoxy group represented by V ¹ and V ² include groups such as methoxy, ethoxy and propoxy. The aryl group represented by V ¹ and V ² may have a substituent at any position,
Examples thereof include phenyl, p-tolyl, p-hydroxyphenyl, p-methoxyphenyl, and other groups. V ¹
And the condensed ring formed by V ² and azole ring together form, for example, benzoxazole, 4,5, 6,
7-tetrahydrobenzoxazole, naphtho [1,2
-D] oxazole, naphtho [2,3-d] oxazole, benzothiazole, 1,3-dioxolo [4,5-
f] benzoxazole, 4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 1,3-dioxolo [4,5-f] benzo Examples of the condensed ring include thiazole, benzoselenazole, naphtho [1,2-d] selenazole, benzoterrazole, thieno [2,3-b] thiazole.

The above-mentioned substituents represented by V ¹ and V ² and the condensed ring to be formed may have a substituent at any position, and as the substituent, for example, the above-mentioned R ² has. Examples of the substituent include the same groups.

The 5- or 6-membered nitrogen-containing heterocyclic group formed by Q represents a group of non-metal atoms necessary for forming a cyclic group by linking with a keto group adjacent to the methine group bonding site.

These cyclic groups are acidic cyclic groups used in known merocyanine dyes, and are specifically isoxazolone type (2-isoxazoline-5-one etc.) and oxazolidine type (2-thio-oxazolidine). -2,4-dione, 2,4-oxazolidinedione, oxazolidin-4-one, 2-oxazoline-4-one, etc., thiazolidine-based (2-thio-thiazolidine-2,4-dione,
2,4-thiazolidinedione, thiazolidin-4-one, 2-thiazolin-4-one, etc., imidazolidine-based (2-thio-imidazolidine-2,4-dione, 2,4
-Imidazolidindione, imidazolidin-4-one,
2-imidazolin-4-one, etc.), selenazolidine-based (2-thio-selenazolidine-2,4-dione, 2,4
-Selenazolidindione, selenazolidin-4-one,
2-selenazolin-4-one etc.), pyridine type (tetrahydropyridine-2,4-dione, tetrahydropyridine-2,6-dione etc.), pyrimidine type (tetrahydropyrimidine-2,4-dione, tetrahydropyrimidine-2, 6-dione, hexahydropyrimidine-2,4
6-trione, 2-thio-hexahydropyrimidine-
2,4,6-trione etc.), pyrazoline type (pyrazolin-5-one, pyrazolidine-3,5-dione etc.), pyrazolopyridine type (pyrazolo [3,4-b] pyridine-
3,6-dione etc.), pyrazolopyrimidine system (pyrazolo [1,5-a] pyrimidin-2-one etc.), pyrazolo [2,3-a] imidazol-6-one etc.) Can be mentioned.

Any group can be substituted at any position on these rings. For example, the substituents (substituted or unsubstituted aryl group, which are mentioned in the concrete explanation of V ¹ and V ²⁾ can be substituted. A substituted or unsubstituted alkyl group, heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, ureido group,
Carbamoyl group, carbamoyloxy group, alkoxycarbonylamino group, aryloxycarbonylamino group, cyano group, acyl group, carboxyl group, phosphoryl group, amide group, imide group, sulfonyl group, sulfinyl group, sulfamoylamino group, sulfamoyl group Or a sulfonamide group).

Further, it may be bonded to another nitrogen-containing heterocyclic group via a methine group at a position other than the above-mentioned methine group of the 5- or 6-membered nitrogen-containing heterocyclic group formed by Q. .

Specific examples of the sensitizing dye represented by the general formula [DI] (hereinafter referred to as the sensitizing dye of the present invention) are shown below, but the invention is not limited thereto.

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

[Chemical 6]

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

The sensitizing dye of the present invention is, for example, FM
Hama, "Cyanine Soybeans and Related
Compounds "(1964, published by Inter Science Publishers), US Pat. No. 2,454,629,
It can be easily synthesized by referring to a conventionally known method described in JP-A-2,493,748 and the like.

Specific synthetic examples are given below, but other exemplified compounds can be synthesized by the same method.

Synthesis Example (Synthesis of Exemplified Compound D-7)

[0045]

Embedded image

Compound (a) 5.1 g and compound (b) 1.
9 g was added to 20 ml of DMSO (dimethyl sulfoxide), and the mixture was heated to 60 ° C. and suspended / stirred. Next, while keeping the reaction temperature at 60 ° C. by adding 3.5 g of piperidine,
The mixture was heated and stirred for another 90 minutes.

The reaction solution was returned to room temperature, ethyl acetate was added to the reaction product, the mixture was stirred and stood still, and then the supernatant liquid was decanted and removed. A mixed solution of ethanol and acetone and acetic acid were added to the remaining viscous material, and the mixture was stirred and crystallized. The crystals were collected by filtration and washed with ethanol. The crude crystals were recrystallized from methanol to obtain 2.1 g of the target D-7. The maximum absorption wavelength of this dye in a methanol solution is 509 nm (ε _max ; 82.0).
00).

The addition amount of the sensitizing dye of the present invention largely depends on the conditions used and the type of emulsion, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ per mol of silver halide.
The amount is more preferably 2 × 10 ⁻⁶ to 2 × 10 ⁻³ mol.

The sensitizing dye can be added to the silver halide emulsion by a conventionally known method. For example, JP-A-50-8
No. 0826, No. 50-80827, the method of adding a protonated solution, U.S. Pat. No. 3,822,135, and the method of dispersing and adding with a surfactant as described in JP-A No. 50-11419, U.S. Pat. 676, 147, 3, 4
69,987, 4,247,627, JP-A-51.
No. 59942, No. 53-16624, No. 53-10.
No. 2732, No. 53-102733, No. 53-137.
No. 131, etc., and a method of adding it as a solid solution described in East German Patent 143,324, or Research Disclosure (R).
D) A water-soluble solvent (such as water, methanol, ethanol, propyl alcohol, acetone or fluoroalcohol) which dissolves a dye represented by 21,802, JP-B-50-40659 and JP-A-59-148053. Low boiling point solvent,
A high boiling point solvent such as dimethylformamide, methyl cellosolve or phenyl cellosolve), or a method of adding it after dissolving it in a mixed solvent thereof is arbitrarily selected and added to the emulsion.

The sensitizing dye may be added at any stage in the emulsion production process from physical ripening to coating after chemical ripening, but it is preferably added between physical ripening and the end of chemical ripening. During physical ripening or in the chemical ripening step, addition prior to addition of the chemical sensitizer or immediately after addition of the chemical sensitizer has the effect of obtaining higher spectral sensitivity, and is preferable.

The sensitizing dye of the present invention can be used in combination with other sensitizing dyes. In this case, each sensitizing dye may be added to the emulsion at the same time or separately at different times, and the order and time interval at that time may be arbitrarily determined depending on the purpose.

Further spectral sensitivity can be obtained by using a sensitizing dye in combination with a compound that exerts a supersensitizing effect. Examples of such a compound having a supersensitizing effect include, for example, U.S. Pat. Nos. 2,933,390 and 3,416,927,
No. 3,511,664, No. 3,615,613, No. 3,615,632, No. 3,635,721, JP-A-3-15042, No. 3-110545, No. 4-2.
Compounds having a pyrimidinylamino group or a triazinylamino group described in JP-A-558441; British Patent 1,13
Aromatic organic formaldehyde condensates described in JP-A-7-580 and JP-A-61-169833; JP-A-4-184
332, the calixarene derivative described in U.S. Pat. No. 4,030,927, and the halogenated benzotriazole derivative described in U.S. Pat. No. 4,030,927;
Bispyridinium compounds described in JP-A-88641 and the like; aromatic heterocyclic quaternary salt compounds described in JP-A-59-191032, electron-donating compounds described in JP-A-60-79348, and U.S. Pat. No. 4,307,183. Polymers containing aminoallylidene malononitrile units described in JP-A-4-14
A hydroxytetrazaindene derivative described in 9937,
Examples thereof include 1,3-oxadiazole derivatives described in U.S. Pat. No. 3,615,633 and amino-1,2,3,4-thiatriazole derivatives described in U.S. Pat. No. 4,780,404.

The supersensitizer may be added at any time according to the above-mentioned photosensitive dye addition time. The addition amount is 1 × 10 ^-6 to 1 per mol of silver halide.
It is selected in the range of × 10 ^-1 mol, and the sensitizing dye is 1/10.
Used at an addition molar ratio of -10/1.

The halogen composition of the silver halide grains according to the present invention may be a mixture of chlorine, bromine and iodine in any ratio, but preferably contains at least 50 mol% of silver chloride and per mol of silver. It contains 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol of an iridium compound. More preferably, the iridium compound is contained in an amount of 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol per mol of silver.

The emulsion according to the present invention is preferable because further high sensitivity can be achieved by combining with the chemical sensitization using at least one selected from a selenium compound and a tellurium compound.

As the silver halide grains, any of spherical grains, cubic crystals, tetradecahedral crystals, octahedral crystals, tabular crystals having an aspect ratio of 5 or more can be used, but "(standard deviation of grain size / Monodisperse particles having a coefficient of variation represented by (average value of particle size) × 100 ”of 15% or less are preferable.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

The average grain size of the silver halide grains is not particularly limited, but is preferably 0.05 to 4.0 μm, more preferably 0.1 to 1.0 μm.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkides, published by P. Glafkides; Chemie et Ph.
isique Photographique, Pau
L Motel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin;
Photographic Emulsion Che
Mistry, FocalPress, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al; Ma).
king and Coating Photograph
hic Emulsion, FocalPress, 1
964) and the like.

As the iridium compound according to the present invention, conventionally known compounds described in, for example, Japanese Patent Publication Nos. 43-4935 and 45-32738 can be used. Specifically, iridium trichloride and iridium tribromide can be used. , Iridium tetrachloride, iridium tetrabromide, hexachloroiridium (II
I) potassium, hexabromoiridium (III) potassium, hexachloroiridium (IV) sodium, hexabromoiridium (IV) potassium and the like,
These may be used alone or in combination of two or more.

The selenium compound according to the present invention is, for example, JP-B-44-15748, JP-A-59-180536,
60-150046, JP-A-4-25832, 4-109240, 4-147250, 4-2.
No. 43249, No. 4-271341, No. 5-1138.
5, conventionally known compounds described in No. 5, No. 5-40324, No. 5-224332, No. 5-224333, etc. can be used, for example, selenourea derivatives, isoselenocyanate derivatives, selenoketone derivatives, selenamide derivatives. , Selenohydrazide derivatives, selenoester derivatives, phosphine selenide derivatives and the like, and the selenium compounds shown below are preferable.

[0062]

Embedded image

The tellurium compound can be obtained, for example, from US Pat.
320,069, 3,772,031, British Patents 1,121,496, 1,295,462, 1,396,696, Journal of Chemicals.
Society Chemical Communication (JC
hem. Soc. Chem. Commun. ), 11
02 (1979), 645 (1979), 63.
Page 5 (1980), Journal of Chemical Society Perkin Transactions (J. Che.
m. Soc. Perkin Trans. ), 1 volume, 2
Conventionally known compounds described on page 191 (1980) and the like can be used, and examples thereof include tellurourea derivatives, isotellurocyanate derivatives, telluroketone derivatives, telluroamide derivatives, tellurohydrazide derivatives, telluroester derivatives, and phosphine telluride derivatives. A tellurium compound is mentioned, Preferably, the tellurium compound shown below is mentioned.

[0064]

Embedded image

The selenium compound and the tellurium compound are used in an amount of 1 × 10 ^-8 to 1 × 10 ^-4 mol, preferably 1 ×, per mol of silver.
10 ⁻⁷ to 1 × 10 ⁻⁵ mol is contained.

The chemical sensitization of the photographic emulsion of the present invention may be combined with sulfur sensitization and / or gold sensitization.

The hydrophilic protective colloid used for preparing the light-sensitive material of the present invention includes, in addition to gelatin used in ordinary silver halide emulsions, gelatin derivatives such as acetylated gelatin and phthalated gelatin, and water-soluble gelatin. Included are cellulose derivatives and other synthetic or natural hydrophilic polymers.

For the photographic material, various techniques and additives known in the art can be used as necessary. For example, in addition to the photosensitive emulsion layer, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer and a backing layer can be provided, and various couplers and high boiling points can be contained in these layers. Solvents, antifoggants, stabilizers, development inhibitors, bleaching accelerators, fixing accelerators, color mixing inhibitors, formalin scavengers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, UV rays An absorber, an anti-irradiation dye, a filter light absorbing dye, a polymer latex, a heavy metal, an antistatic agent, a matting agent and the like can be contained by various methods.

As the support that can be used for the light-sensitive material, cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper,
Examples include paper laminated with polyethylene and the like, glass, metal and the like. These supports are subjected to an undercoating process if necessary.

More specifically, the above-mentioned various additives are R
D, 176, 17643 (December 1978), 1
84, 18431 (August 1979) and 187.
Vol., 18716 (November 1979).

To develop the light-sensitive material of the present invention, for example, T.I. H. The Theory of the Writer by James
Photographic Process 4th Edition (The The
ory of the Photographic P
process, fourth Edition) 291-
334 pages and the Journal of the American Chemical Society (J. Am. Chem. So
c. ), 73, p. 3100 (1951) can be effectively used.

[0072]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) Using a silver iodobromide (silver iodide content of 2 mol%) seed emulsion having an average grain size of 0.1 μm, an aqueous ammoniacal silver nitrate solution and potassium bromide were prepared. An aqueous solution and an aqueous solution of potassium iodide were added by the double jet method to grow a cubic monodisperse emulsion of silver iodobromide (average silver iodide content: 1.2 mol%) having an average grain size of 0.34 μm. The modified gelatin treated with natto was desalted by the flocculation method and then dispersed in gelatin. The variation coefficient of the grain size of the obtained silver halide grains was 0.17.

The pH of this emulsion was adjusted with citric acid and sodium chloride.
After adjusting the pAg to 5.8 and the pAg to 7.0, the additives shown in Table 1 were added, and the stabilizer (T- was added after optimal chemical aging at 60 ° C using ammonium thiocyanate and chloroauric acid).
600 mg per 1 mol of silver was added to 1) to stop ripening, the temperature was returned to 40 ° C., and the sensitizing dyes shown in Table 1 were added.

T-1: 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene (Preparation of Silver Halide Emulsion B) Using the same seed emulsion as Emulsion A, silver nitrate aqueous solution, potassium bromide aqueous solution and potassium chloride aqueous solution were added by double jet method to obtain grains. After growing, desalted by a flocculation method using modified gelatin treated with phenyl isocyanate and dispersed in gelatin to obtain silver chloroiodobromide having an average particle size of 0.36 μm (silver chloride content 60%). An emulsion consisting of cubic monodisperse grains (variation coefficient 0.1) of mol%, silver iodide content of 0.5 mol%, and others silver bromide) was obtained.

The pH of this emulsion was adjusted with citric acid and sodium chloride.
After adjusting the pAg to 5.8 and the pAg to 7.0, the additives shown in Table 1 were added, and optimal chemical ripening was performed at 60 ° C. using ammonium thiocyanate and chloroauric acid, and then T-1 was silver. 1
Aging was stopped by adding 600 mg per mole.

(Preparation of photosensitive material) As a backing layer,
400 g of gelatin, 2 g of polymethylmethacrylate having an average particle size of 6 μm, 24 g of potassium nitrate, 6 g of sodium dodecylbenzenesulfonate, the following antihalation dyes F-1, F-2 and F-3 (used together at a 2: 1: 1 molar ratio).
A backing layer coating solution comprising 20 g of a dye emulsion dispersion equivalent to 2 g / m ² and a hardening agent H-1 (glyoxal) was prepared, and a glycidyl methacrylate / methyl acrylate / butyl methacrylate copolymer (50: 1) was prepared.
(0:40 weight ratio) was diluted to a concentration of 10 wt% to obtain an aqueous copolymer dispersion, which was coated as a subbing liquid on one side of a polyethylene terephthalate (PET) film. A backing-backed support obtained by coating with a protective layer solution containing an agent, H-1, and sodium dodecylbenzenesulfonate was prepared.

The coating amount of each of the backing layer and the protective layer is
The amount of gelatin applied is 2.0 g / m ² .

[0079]

Embedded image

On the backed support, two emulsion coating solutions and a protective layer coating solution having the following formulations were simultaneously coated in two layers with a slide hopper to obtain light-sensitive material samples (1 to 30).

The coating amount of the emulsion layer is 3.0 / in terms of silver amount.
m ² , the amount of gelatin is 2.5 g / m ² , and other additives are
The amounts are per mol of silver halide, the protective layer has an amount of gelatin of 0.9 g / m ² , and the additive has an amount of m ² per m ² .

Formulation (1): silver halide emulsion layer composition gelatin 2.5 g silver halide emulsion A or B 3.0 g sensitizing dye (shown in Table 1) 4.5 × 10 ⁻⁴ mol nitrophenyl triphenylphosphonium Chloride 30 mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 1.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg 2-Mercaptobenzothiazole 10 mg Trimethylolpropane 9.0 g 1,1-Dimethylol-1-bromo -1-Nitromethane 10 mg C ₄ H ₉ OCH ₂ CH (OH) N (CH ₂ COOH) ₂ 1.0 g Inhibitor (ST-1) 35 mg Inhibitor (ST-2) 60 mg Formulation (2): emulsion protective layer composition Gelatin 0.9 g Surfactant (SA-1) 10 mg Surfactant (SA- ) 10 mg Matting agent (monodisperse silica having an average particle size of 3.5 μm) 3 mg Hardener (H-2) 40 mg SA-1: Di (2-ethylhexyl) sulfosuccinate / sodium salt SA-2: Disulfosulfosuccinate (2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptyl) -sodium salt H-2: 1,3-vinylsulfonyl-2-propanol

[0083]

Embedded image

(Evaluation of Photographic Performance) A wedge was attached to each of the obtained samples, and the Ratten filter No. 98 and a Toshiba color glass filter Y-48 (Y filter) are applied to expose each for 10 ^-2 seconds to obtain a developing solution XD having the following composition.
-SR and fixing solution XF-SR were charged in an automatic processor SRX-502 (manufactured by Konica) for rapid processing under the following conditions.

An optical densitometer PDA-65 was used as the processed sample.
The density is measured with (made by Konica), and the fog density +
The reciprocal of the exposure amount at 0.3 was taken, and the ratio of the sensitivity (S _Y ) obtained by exposing yellow light to the sensitivity (S _B ) obtained by exposing blue light was obtained.

For the residual color, the unexposed film was developed and fixed, and the residual color when five sheets were overlaid was visually evaluated on a five-point scale. The highest rank is "5" when there is no residual color, and the rank is sequentially reduced to "4", "3", "2" and "1" according to the degree of occurrence of residual color. .

(Preparation of Processing Agent) Developer A Part-A (for 38 liter finish) Potassium hydroxide 1140 g Potassium sulfite 2451 g Sodium hydrogen carbonate 380 g Boric acid 38 g Diethylene glycol 418 g Diethylenetriamine pentasodium pentasodium 61 g 5-Methylbenzotriazole 1.9 g Hydroquinone 1064 g Add water to finish to 9.3 L Part-B (for 38 L finishing) Glacial acetic acid 562 g Triethylene glycol 418 g 1-Phenyl-3-pyrazolidone 100 g 5-Nitroindazole 9.5 g 50 L tank at 25 ° C. Add 20 liters of water,
Charge Part-A with stirring, then Part-
B was added and finally made up to 38 liters with water. This developing solution was allowed to stand at 25 ° C. for 24 hours, and then the pH was adjusted to 10.53 at 25 ° C. with potassium hydroxide or acetic acid.

Starter glacial acetic acid 230 g Potassium bromide 200 g Water is added to make up to 1.5 liters.

The above developer was used as it was as a replenisher, and a starter was added to the solution in the development processing tank at the start of use at a rate of 20 ml per liter of the above developer.

The developing replenisher is ² per 1 m ² of the light-sensitive material sample.
Make up 50 ml.

Fixer Part-A (for 38 liter finish) Ammonium thiosulfate 6080 g Ethylenediaminetetraacetic acid disodium dihydrate 0.76 g Sodium sulfite 456 g Boric acid 266 g Sodium hydroxide 190 g Glacial acetic acid 380 g Water is added to make 9.5 liter. .

Part-B (for 38 liter finishing) Aluminum sulfate (calculated as anhydrous salt) 380 g Sulfuric acid (50 wt%) 228 g Water is added to finish to 1.9 liter.

20 liters of water at 20 ° C. was placed in a 50 liter tank, and the above Part-A and Par were stirred.
t-B was sequentially added, and finally water and acetic acid were added to make 38 liters, and the pH was adjusted to 4.30 at 25 ° C. (fixing solution 1
Al ³⁺ content per liter is 58.5 mmol).

(Development processing) The development processing is performed by an automatic developing machine (SR
X-502) in a 45-second processing mode, using the above-mentioned developing solution and fixing solution, developing at 35 ° C. for 15 seconds and fixing for 33 seconds.
The treatment was performed at 15 ° C. for 15 seconds, and the results are shown in Table 1.

[0095]

[Table 1]

[0096]

Embedded image

From Table 1, the light-sensitive material according to the present invention is superior to the comparative sample in terms of residual color contamination, high spectral sensitivity can be maintained without increasing fog density, and good photographic performance can be provided. I understand.

Example 2 (Preparation of Silver Halide Emulsion C) A silver chloroiodobromide (silver chloride 20 mol%, silver iodide 0.5 mol%, other silver bromide) emulsion was prepared by the simultaneous mixing method. Prepared.

Denatured gelatin treated with phenyl isocyanate was desalted by the flocculation method and then dispersed in gelatin. A mixture of compounds A, B and C was added as a mildew-proofing agent to give an average particle size of 0. An emulsion consisting of cubic monodisperse grains (variation coefficient 10%) of 0.3 μm was obtained.

The pH of this emulsion was adjusted with citric acid and sodium chloride.
Of the inhibitor (ST-3) and the stabilizer (T-1) after adjusting the pAg to 5.8 and the pAg to 7.0, and then adding the additives as shown in Table 2 and optimally performing chemical aging at 55 ° C. ) Was added to 60 mg and 600 mg per 1 mol of silver to stop the ripening.

ST-3: 1-phenyl-5-mercaptotetrazole

[0102]

Embedded image

(Preparation of silver halide emulsion D) Silver chloroiodobromide (silver chloride 20 mol%, silver iodide 0.5
Mol%, others silver bromide) emulsions were prepared.

During the mixing process from the formation of 5% of the final reaching average particle size to the reaching of the final reaching average particle size, K ₂ IrC
l ₆ was added 8 × 10 ^-7 mole per silver mole. Desalted by flocculation method using modified gelatin treated with phenyl isocyanate, and then dispersed in gelatin,
A mixture of compounds A, B and C was added as an antifungal agent, and cubic monodisperse particles with an average particle size of 0.3 μm (variation coefficient 10%)
An emulsion consisting of

The pH of this emulsion was adjusted with citric acid and sodium chloride.
Of the inhibitor (ST-3) and the stabilizer (T-1) after adjusting the pAg to 5.8 and the pAg to 7.0, and then adding the additives as shown in Table 2 and optimally performing chemical aging at 55 ° C. ) Was added to 60 mg and 600 mg per 1 mol of silver to stop the ripening.

(Preparation of silver halide emulsion E) Silver chloroiodobromide (silver chloride 50 mol%, silver iodide 0.5
Mol%, others silver bromide) emulsions were prepared.

During the mixing process from the formation of 5% of the final reaching average particle size to the reaching of the final reaching average particle size, K ₂ IrC
l ₆ was added 8 × 10 ^-7 mole per silver mole. Desalted by flocculation method using modified gelatin treated with phenyl isocyanate, and then dispersed in gelatin,
A mixture of compounds A, B and C was added as an antifungal agent, and cubic monodisperse particles with an average particle size of 0.3 μm (variation coefficient 10%)
An emulsion consisting of

The pH of this emulsion was adjusted with citric acid and sodium chloride.
Of the inhibitor (ST-3) and the stabilizer (T-1) after adjusting the pAg to 5.8 and the pAg to 7.0, and then adding the additives as shown in Table 2 and optimally performing chemical aging at 55 ° C. ) Was added to 60 mg and 600 mg per mol of silver to stop the ripening.

(Preparation of Photosensitive Material) Thickness of 0.1 μm on Both Sides
An emulsion layer of the following formulation (11) was prepared by adding an emulsion layer of the following formulation (11) on one undercoat layer of a PET film having a thickness of 100 μm and having an undercoat layer (described in Example 1 of JP-A-59-19941). Is 2.0 g / m ² and the amount of silver is 3.2 g / m ^2, and an emulsion protective layer of the following formula (12) is further applied thereon so that the amount of gelatin is 1.0 g / m ^2. And a backing layer according to the following formulation (13) so that the amount of gelatin would be 2.4 g / m ² , and then further coated on the other undercoat layer on the opposite side. Photosensitive material samples (31 to 58) were obtained by coating the backing protective layer of the formulation (14) so that the amount of gelatin was 1.0 g / m ² . The coating amount of each additive is shown per m ² of the photographic material.

Formulation (11): Silver halide emulsion layer composition Gelatin 2.0 g Silver halide emulsion (listed in Table 2) 3.2 g Sensitizing dye (listed in Table 2) 3.0 × 10 ⁻⁴ mol Stabilizer (T -1) 30 mg Antifoggant (adenine) 10 mg Antifoggant (ST-3) 5 mg Surfactant (saponin) 0.1 g Surfactant (SA-3) 8 mg Hydrazine derivative (NU-1) 35 mg Nucleation accelerator (NA-1) 70 mg Latex polymer (Lx-1) 1.0 g Polyethylene glycol (molecular weight 4000) 0.1 g Hardener (H-3) 60 mg SA-3: Sodium sulfosuccinate (i-amyl decyl) sodium Salt H-3: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0111]

Embedded image

Formulation (12): Emulsion protective layer composition Gelatin 0.9 g Surfactant (SA-1) 10 mg Surfactant (SA-2) 10 mg Matting agent (monodisperse silica having an average particle size of 3.5 μm) 3 mg Hard Film agent (H-2) 40 mg Formulation (13): Backing layer composition Gelatin 2.4 g Surfactant (saponin) 0.1 g Surfactant (SA-3) 6 mg Colloidal silica 100 mg Antihalation dye (F-1) 30 mg Antihalation Dye (F-2) 75 mg Antihalation Dye (F-3) 30 mg Formulation (14): Backing Protective Layer Composition Gelatin 1.0 g Surfactant (SA-1) 10 mg Matting Agent (average particle size 5.0 μm Monodisperse PMMA) 50 mg Hardener (H-1) 35 mg Each of the obtained samples was divided into two parts, one was left as it was, and the other was heated at high temperature. The sample was subjected to 20% RH for stability evaluation under
-Forcibly deteriorated by leaving it in an environment of 50 ° C for 3 days.

(Evaluation of Photographic Performance) Each of the obtained samples was adhered to a wedge and the Ratten filter No. It was exposed to light for 10 ^-5 seconds via a ^No. 21 and processed by an automatic processor GR-26S (manufactured by Konica) for rapid processing in which a developing solution and a fixing solution having the following compositions were added.

An optical densitometer PDA-65 was used as the processed sample.
The density was measured with (manufactured by Konica Corp.), and the sensitivity was measured by the reciprocal of the exposure amount at the fog density + 0.3 according to the usual method, and the sensitivity of the sample immediately after coating / drying of the sample 31 was taken as 100 and shown as a relative value.

Further, the residual color contamination rank is the same as the first embodiment in the five-level evaluation. Ranks "2" and "1" are levels that are not practically preferable.

Developer potassium sulfite 60.0 g Hydroquinone 15.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 0.5 g Potassium carbonate 50.0 g Potassium bromide 5.0 g 2-mercaptobenzimidazole 0.25 g 5-methylbenzotriazole 0.4 g Water was added to make 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide.

Fixer (composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17.0 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium oxalate dihydrate 2. 0 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 8.5 g Fixing At the time of using the liquid, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter and used. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) Process Temperature Time Image 38 ° C. 20 seconds Fixing 35 ° C. 20 seconds Washing 30 ° C. 15 seconds Drying 50 ° C. 15 seconds The results are summarized in Table 2.

[0119]

[Table 2]

As is apparent from Table 2, the light-sensitive material according to the present invention gave good photographic performance in which fogging and sensitivity fluctuation were suppressed as compared with the comparative sample. This effect was remarkably observed in a silver halide photographic emulsion containing a water-soluble iridium salt compound and having a high silver chloride composition.

Further, it can be seen that the compound of the present invention is superior to the comparative compound in terms of residual color contamination.

[0122]

According to the present invention, a silver halide photographic light-sensitive material having improved spectral sensitivity in the wavelength region from green to red and improved residual color contamination can be obtained.

Claims (3)

[Claims] 1. A silver halide grain characterized in that at least one of the silver halide emulsion layers contains silver halide grains spectrally sensitized with a compound represented by the following general formula [DI]. Photographic material. Embedded image [In the formula, Y represents an imino group which may have a substituent, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, and Q represents an atom group which completes a 5- or 6-membered nitrogen-containing heterocycle. ,
The nitrogen-containing heterocycle has a substituent. R ¹ represents an aliphatic group having 10 or less carbon atoms substituted with a water-solubilizing group, and n represents 0 or 1. When n = 0, R ² represents an aralkyl group, and n
When = 1, R ² represents an alkyl group, an aryl group or an aralkyl group. V ¹ and V ² each represent a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. In addition, V ¹ and V ² may be bonded to each other to form a condensed ring which may have a substituent. ] 2. Silver halide grains spectrally sensitized with at least one compound represented by the general formula [DI] are 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol per mol of silver. Containing at least 50 mol% of an iridium compound
2. The silver halide photographic light-sensitive material according to claim 1, which is a silver halide grain containing silver chloride. 3. A silver halide grain spectrally sensitized with at least one compound represented by the general formula [DI] is chemically sensitized with at least one compound selected from a selenium compound and a tellurium compound. 3. The silver halide photographic light-sensitive material according to claim 1 or 2, which is a silver halide grain.