JPS5891445A - Photographic silver halide emulsion - Google Patents

Abstract

PURPOSE:To increase the sensitivity of a negative photographic emulsion in the blue light range and to prevent the sensitivity change due to a dead coating liq. by hypersensitizing the emulsion with 2 kinds of specified sensitizing dyes. CONSTITUTION:To a negative photographic emulsion are added a sensitizing dye represented by general formulaI(where each of Z11 and Z12 is a group of atoms required to form a ring such as benzoxazole, benzothiazole, benzoselenazole, benzimidazole, pyridine or quinoline, each of R11 and R12 is alkyl, alkenyl or aryl, R3 is H, methyl or ethyl, X 1is an anion, and l is 0 or 1) and a sensitizing dye represented by general formula II (where Z21 is a group of atoms required to form a ring such as benzoxazole, benzothiazole or benzoselenazole, Z22 is a group of atoms required to form a ring such as rhodanine, 2-thiohydntoin or 2- thioselenazoline-2,4-dione, and each of R21 and R22 is alkyl, alkenyl or aryl).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to spectrally sensitized, particularly supersensitized, negative-working silver halide photographic emulsions, and more particularly to blue light (approximately 400
= 500 nm) negative m superchromically sensitized in the wavelength range
This invention relates to silver halide photographic emulsions.

It is well known that adding a sensitizing dye to a silver halide photographic emulsion expands the sensitive wavelength range of the silver halide emulsion and spectrally sensitizes it. It is also known to use two or more types of sensitizing color chips in combination for sensitization. When two or more sensitizing dyes are used in combination, the spectral enhancement and sensitization are often intermediate or reduced compared to the effects of the individual dyes used alone, but different types of sensitization The use of certain particular combinations of dyes can significantly increase the spectral sensitivity over the use of each sensitizing dye alone. This phenomenon is usually called the supersensitizing effect of the sensitizing dye.

In this way, by using a combination of sensitizing dyes, higher spectral sensitivity can be obtained than when each sensitizing dye is used alone, and the sensitizing wavelength range that matches the intended use of the photographic material can be obtained. The discovery of a combination of sensitizing dyes that can be obtained has become a major SGM in the spectral sensitization technology of silver halide photographic emulsions.

Generally, during the production of silver halide photographic light-sensitive materials, after preparing the coating solution for the silver halide photographic emulsion, up to the coating process,
In some cases, it is stored at a high temperature suitable for coating, but in this case, the sensitivity changes as the storage time increases, leading to sensitivity variations within the same lot from an industrial perspective, which is a serious problem. This one-time change can be broadly classified into two types: causes related to the sensitizing dye, and causes related to the silver halide grain KM. What is attributed to the sensitizing dye is the coupler t
-This is particularly noticeable in silver halide emulsions containing. However, sensitizing dyes and couplers are indispensable in photographic technology, and there is a strong desire to establish technology for couplers using sensitizing dyes without interlayers as described above.

In addition, the combination technology of two or more sensitizing dyes in the blue light region is
Some have already been disclosed. For example, JP-A-51-
A supersensitizing technique using a sensitizing dye having a naphthoselenazole or naphthothiazole IM and a sensitizing dye having an imidazole nucleus, a benzimidazole nucleus, or a natuthothiazole nucleus described in JP-A No. 29128, or JP-A-51-7 Supersensitization technology using a combination of a sensitizing dye having a natuthothiazole nucleus or a naphthoselenazole@ and a sensitizing dye having a thiazole nucleus, a benzothiazole nucleus, or a benzoselenazole nucleus is known. However, these techniques have not yet achieved sufficiently desirable photographic performance. In other words, not only does it not satisfy the basic condition of obtaining the necessary sensitization effect in the required wavelength range, but it also sensitizes undesirable wavelength ranges, or the coating of silver halide photographic emulsions There are problems such as severe changes in sensitivity during high-temperature storage.

Furthermore, in Japanese Patent Publication No. 8855-35386, monomethine cyanine dyes having a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a naphthonazole nucleus, a pyridine nucleus, and a quinoline nucleus are described. Toko tL nucleus, a-danine nucleus, 2-thioxazoline-2,4-dione nucleus, 2
-Thioselenazoline-2,4-dione in a supersensitizing combination with a merocyanine dye, it is possible to obtain high sensitivity in internally substituted direct-positive distilled silver halide, and also to achieve low sensitivity, which is common in this type of emulsion. The emulsions used as O internal lIFgl type emulsions, which are said to improve the disadvantages of maximum concentration and high minimum density, include the converged emulsion of Kigeki No. 2,592,250, and the Metal ion doping emulsion described in No. 52-34213, JP-A No. 50-8524, JP-A No. 50-38525
There are emulsions of silver chloride and silver bromide deposited in a layered manner as described in the above publication. These emulsions have a photosensitive site inside them, and even if the surface is chemically ripened, the degree of chemical ripening is very small. It is impossible to predict what kind of effect it will have on the photosensitive nuclei existing on the surface generated as a result. Similarly, it is impossible to measure changes in performance of the coating solution during stagnation at high temperatures, which are thought to be due to interactions between substances coexisting in the coating solution and photosensitive nuclei.

In order to prevent sensitivity changes during high-temperature storage, for example, a method of adding an azaindene compound known as a stabilizer, a method of adding a reducing agent such as hydroquinones or sulfinic acids, or JP-A-49-111629 If a specific copolymer and a fluorescent brightener are used in combination, as described in 2003, these techniques will be even more effective.

Therefore, the first object of the present invention is to provide a negative silver tetragnate emulsion having high blue sensitivity.
The object of the present invention is to provide a negative II/' silver halide photographic emulsion that exhibits small sensitivity fluctuations due to stagnation of the coating solution at high temperatures.

The above purpose was achieved by the following general formula [!] through intensive research by the present inventors. ] and at least one sensitizing dye represented by the following general formula (1) where 2. and zu are respectively benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, natuthiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzimidazole nucleus, naphthoxazole nucleus, pyridine nucleus or quino9ffm! Represents the atomic group necessary to form. , and Otori and Hiro each represent an alkyl group, an alkenyl group, or an aryl group, and ~ represents a hydrogen atom, a methyl group, or an ethyl group. Appetizers are represented by 鈨 ions, and I represents O or 1t-.

General formula LID Here, forms a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a nathothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzimidazole nucleus, or a represents the atomic group necessary for The pigs are p-danine nuclei,
2-Thiohydantoin or 2-Thioselenazoline-
Represents an atomic group necessary to form 2,4-dione, and 41 and R□ are alkyl groups, alkenyl groups, or L
◇ represents an aryl group Furthermore, as a preferred example of the general formula LD, the following general formula LID' is more advantageously used as a preferable example of the general formula (I) (Z) and among the general formula LIE).

General formula [■]' where - and 2. are each independently necessary to form a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a pyridine nucleus, a quinoline nucleus, a benzimidazole nucleus, or a naphthoxazole nucleus. represents a two-atomic group.

Rsi and ~ each independently represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably an alkyl group substituted with a carboxyl group or a sulfo group. Preferred are carbon atoms and sulfoalkyl groups of 1 to 4 atoms. R
, is selected from a hydrogen atom, a methyl group, and an ethyl group, and X? represents an anion, and 1 represents 0 or 1.

Furthermore, zu and 2. may each be substituted with a substituent, and preferred substituents are a hydrogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group, or an alkoxycarbokyl group. More preferred substituents are a halogen atom, a cyano group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred are a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, or It is an ethoxy group.

General formula up' where -1 is a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a benzoselenanol nucleus,
Naphthoselenazole core, benzimidazole core or,
Represents the atomic group necessary to form the naphthoimidazole nucleus. Further, z21 may be substituted with various substituents, and preferred substituents are a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group. More preferable substituents include a halogen atom, a cyano group, an aryl group, and a carbon number of 1 to 1.
6, an alkyl group (eg, methyl group, ethyl group) or an alkoxy group (eg, methoxy group, ethoxy group).

Z, represents an atomic group necessary to form a 2-thiohydantoin nucleus and a 2-thioselenazoline-2,4-dione nucleus. In the case of the 2-thiohydantoin nucleus, the nitrogen atom at the 1st position may be substituted with -Fi, and preferred substituents are an alkyl group, a hydroxyalkyl group, or an alkoxycarbonyl group. or aryl groups, and preferred substituents that may be substituted are alkyl groups and aryl groups, more preferably alkyl groups having 1 to 4 carbon atoms, sulfoalkyl groups, carboxyalkyl groups, and aralkyl groups. (for example, benzyl group), alkoxyalkyl group (for example, 2-methoxyethyl group, 3-methoxypropyl group), or alkoxydicarbonylalkyl group (for example, methoxycarvinylpropyl group). Particularly preferred is carbon number 1-4.
an alkyl group, a sulfoalkyl group, or an L-benzyl group, but it is most preferable that one is a sulfoalkyl group and the other is an alkyl group.Furthermore, in the present invention, the sensitizing dye represented by the general formula [13'] Among these, a more preferred sensitizing dye is a sensitizing dye represented by the general formula tU+.

General formula [I Here, 4 represents an atomic group necessary to form a benzothiazole nucleus, a benzoselenazole nucleus, or a naphthoshidizole nucleus, and represents a selenium atom, and zIj is When a naphthothiazole or naphthoselenazole nucleus is formed, it represents a sulfur atom, a selenium atom, an oxygen atom or a nitrogen atom. Furthermore, the two cyanine heteropolymers may be substituted with a substituent as shown in the general formula [■]'. Furthermore, R8-1R
1841 is a general formula [! ] It is the same as that shown in '.

In the present invention, among the sensitizing dyes represented by the general formula (I[), particularly useful dyes are those represented by the general formulas.

General formula LV) Here, Δ represents an atomic group necessary to form a benzothiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, or a naphthoxazole nucleus, and Y represents a sulfur atom or a selenium atom. represent. The two cyanine tetrahero ring nuclei are substituted with substituents as shown in the general formula (f), and have the same general formula (as shown in ti). be.

Among the sensitizing dyes represented by the general formula LV3, particularly useful dyes are the sensitizing dyes represented by the general formula LV3.

Here, Y8 represents a sulfur atom or a selenium atom.

In addition, the two cyanine heterocyclic nuclei are OR1m, which may be substituted with a substituent as shown in the general formula ([)k, ~
, R1, and l are the same as those shown in the general formula [■]'.

Among the sensitizing dyes represented by the general formula [P], particularly useful dyes are the sensitizing dyes represented by the general formula [P].

General formula stone] Here 2. are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus,
Represents the atomic group necessary to form the naphthothiazole nucleus or selenazol 1M4.
2*p' In the case of a benzoxazole nucleus, benzothiazole nucleus or benzoselenazole nucleus, the expression is a sulfur atom, a xylene atom, and when 2u forms a naphthol view, a naphthothiazole nucleus or a naphthoselenazole nucleus,
It represents a sulfur atom, a selenium atom or a nitrogen atom, and this nitrogen atom may be substituted with a substituent as shown in the general formula [R5]. Further, R2 and R1□ are each the same as shown in general formula (II).

Among the sensitizing dyes represented by the general formula Jun, particularly preferred are the sensitizing dyes represented by the general formula (capital).

General formula (VD) Here, B1 represents an oxygen atom, a sulfur atom, or a selenium atom. < ,
``at'' and Rfi are each the same as described in general formula (9).

Specific examples of the dyes used in the wAK of the present invention are shown below.

However, the invention is not limited to these dyes.

General formula [[] -1 -3 -5 -6 LIMB [-15 General 2 f-3 1-4 (OHLχaONt OHMs ■-6 I-7 ■-8 Sensitive dye and general formula LI
The sensitizing dye represented by I) is a known one, for example,
Arrival at AirM 8-Mar, The Chemistry Op Heterocyclic Comparin y (Th@Oh@m1s
try of H@tsrocycloo Oonpo
umds) No. 1841f @ Cyanin Gui &.
Related Compound (The 0yanin@
Dr@an+I R@lata10om)ounds
) (NWsissberger ad engineering nt+er
sceDos new publication M@W fork 1964) can be easily synthesized by the method described in K.

The maximum concentration of sensitizing dye used can be determined according to methods known to those skilled in the art.

For example, by dividing the same emulsion and making each emulsion contain a different concentration of sensitizing dye and measuring the sensitivity of each emulsion, supersensitization can be obtained between the dye expressed by the dye expressed by the general formula 11I) and the dye expressed by the general formula 11I). Advantageous proportions of amounts are from 2Q/1 to l/20, in particular from 10/l to l/10.

Methods well known in the art can be used to add the sensitizing dye to the emulsion.

For example, these sensitizing dyes can be directly dispersed in emulsions or dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents). In some cases, it is diluted with water, and in other cases it is dissolved in water, and these solutions! I) can be added to the emulsion at 8.

In addition, ultrasonic vibration is often used for this melting. Furthermore, dyes can be prepared by a method of dissolving the dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in US Pat. No. 3,469,987. . As described in Japanese Patent Publication No. 46-24185, a method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion. Also, the pigment is 1lfII! It can be added to the emulsion in the form of a dispersion by the dispersion method. Other additions to emulsions include U.S. Pat. Nos. 2,912,345 and 3,34.
No. 2,605, No. 2,996,287, No. 3.4
In the present invention, the sensitizing dye lines to be contained in combination are dissolved in the same or different solvents, and the sensitizing dye lines to be contained in combination are dissolved in the same or different solvents and then added to the silver halide emulsion. Solution tl - May be mixed or added separately. When added separately, the order, time and interval can be arbitrarily determined depending on the purpose. The sensitizing dye according to the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but preferably during or after chemical ripening.

The emulsion used in the present invention is a negative emulsion, and is a so-called surface latent image type emulsion that mainly forms a latent image on the grain surface. The term "surface latent image type emulsion" is a term representing a concept corresponding to the term "internal latent image type emulsion" defined, for example, in Japanese Patent Application Laid-Open No. 47-32814.

In the case of negative-working emulsions, photographic images used in practical use are emulsions in which the WE density increases as the amount of light irradiated to the photographic emulsion increases. Of course, such an emulsion also causes a phenomenon called solarization, in which the photographic image density is reversed due to excessive exposure, but this is a phenomenon caused by an exposure that is higher than that used in practical use, and there is no interlayer formation. The silver halide used in the present invention has (1
It can be preferably used whether it has a 00) plane, a (111) plane, or both.

The size of the silver halide grains used in the present invention can be any size within the commonly used range, but it is preferable that the average grain size #t of the grains is 0.05 μm to 1.0 μm, and the grain size distribution may be so-called polydisperse or monodisperse, but monodisperse emulsions are more preferably used.

The silver halide grains used in the present invention can be prepared by methods commonly used by those skilled in the art. These methods are described, for example, in Mies' Theory of Photographic Processes.
theory of Photography.

It can be prepared by various methods such as the ammonia method, the neutral method, and the acid method described in books such as Proo@ss; Mae Mutton, 4th edition). A preferred method is to mix a water-soluble silver salt and a water-soluble halide compound in the presence of a suitable quaternide, and during the precipitation of the silver halide, the temperature, PAg s PH value is adjusted to a suitable value. Preferably, the value is controlled.

The silver halide emulsion according to the present invention may or may not be subjected to salt ripening. Silver halide emulsion is
Water-soluble salts are usually removed after precipitate formation or physical ripening, and the means used for this purpose are as follows:
Even if the long-known Nudel water washing method is used, 1m of inorganic salts with polyvalent anions (e.g. ammonium sulfate, magnesium sulfate), anionic surfactants, polystyrene sulfonic acid, other anionic polymers, or aliphatic- or Precipitation method (flocculation) using gelatin derivatives such as aromatic-acylated gelatin
- It's good to use.

The silver halide emulsion used in the present invention can be chemically ripened by a method commonly practiced by those skilled in the art. For example, the method described in the above-mentioned book "The Theory of Photography Process" by Mies, K113, or various other conventionally known methods can be used. That is, sulfur-containing compounds that can react with silver ions, such as thiosulfur sI #1 or U.S. Pat.
No. 47, No. 2.410,689, No. 3,189,
458, Sol. 313, French Patent No. 2.059.245, etc.
or a sulfur sensitization method using activated gelatin, and also reducing substances such as the sl tin salt described in U.S. Pat. No. 2,487,850; No. 925, No. 2,521,926
No. 2,419,973, No. 2,419,97
Amines described in No. 5, etc., U.S. Patent No. 2,98
3,610, the silane compound described in Japanese Patent No. 2,694,637, or the Journal of Photographic Science (Journal of Photographic Science).
aphia8ai*no* ) Volume 1 (1=953)
A reduction sensitization method such as the method of H, W, Wood described on pages 163 et seq., or U.S. Pat. No. 2,399,
Gold sensitization method using a total complex salt or gold thiosulfate complex described in No. 083, or U.S. Patent No. 2,448,060,
Same No. 2.540゜086, Same No. 1!12,566.24
Sensitization methods using alloys, salts of noble metals such as palladium, rhodium, and ruthenium, as described in No. 5, No. 112,566, No. 263, etc., can be used alone or in combination. Also, instead of or with a sulfur sensitizer, U.S. Patent No. 3,297,446
It is also possible to use the selenium sensitization method described in No.

In the emulsion used in the present invention, gelatin is used as a protective colloid, and sometimes inert gelatin is advantageous.Also, instead of gelatin, a photographically inert gelatin derivative (
phthalated gelatin), water-soluble synthetic polymers (such as phthalated gelatin), water-soluble synthetic polymers (
For example, polyvinyl acrylate, polyvinyl alcohol, polyvinyl pyridone, polyvinyl alkino acid clay,
sulfoxymethyl cellulose, hydroxymethyl cellulose, etc.) can also be used.

In the silver halide emulsion according to the present invention, tetrazaindenes are added for the purpose of preventing caprinin during the manufacturing process, during storage of the light-sensitive material, or during storage, or to stabilize photographic performance. , mercaptotetrazoles and the like may also be included.

It may be a photographic light-sensitive material, or it may be a so-called external color photographic material in which a coupler is supplied during development processing. Furthermore, a black and white photosensitive material using a silver image as the final image may also be used.

The coupler contained in the light-sensitive material comprising the photographic emulsion according to the present invention is a coupling product formed by a coupling reaction with an oxidized form of a developing agent and having a maximum spectral absorption wavelength in a wavelength range longer than 340 am. Although any compound can be used, particularly representative ones include those shown below.

A typical coupler that forms a coupling product having a maximum spectral absorption wavelength in the wavelength range from 350 nm to 50011!1 is known to those skilled in the art as a so-called yellow coupler, for example, as disclosed in U.S. Pat. ，
No. 186,849, No. 2,322,027, No. 2
, No. 728,658, No. 2,875,057, No. 3,265,506, No. 3,277.155, No. 3,408,194, No. 3,415,652
No. 3,447,928, No. 3.664
．． No. 841, No. 3,770,446, No. 3.77
8.277, 3,849,140, 3,8
British Patent No. 94,875, British Patent No. 778,089, British Patent No. 808,276, British Patent No. 875.476, British Patent No. 1,4
No. 02,511, No. 1,421,126 and No. 1
, 513.832 and Japanese Patent Publication No. 1983-135
No. 76, JP-A-48-29432, JP-A No. 4g-6683
No. 4, No. 49-10736, No. 49-122335, No. 50-28834, No. 50-132926, No. 50-138832, No. 51-3631, No. 51-
No. 17438, No. 51-26038, No. 51-260
No. 39, No. 51-50734, No. 51-53825, No. 51-75521, No. 51-89728, No. 5
No. 1-102636, No. 51-107137, No. 51
-117031, 51-122439, 51-
No. 143319, No. 53-9529, No. 53-8
No. 2332, No. 53-135625, No. 53-145
No. 619, No. 54-23528, No. 54-48541
No. 54-65035, No. 54-133329,
It is described in the same magazine No. 55-598, etc.

Typical couplers that form a coupling product t having a maximum convergent wavelength in the wavelength range of 500 mm to 600 nm are those known in the art as magenta couplers, for example, as described in U.S. Pat. 1,
No. 969,479, No. 2,213,986, No. 2
, 294,909, 2.338,677, 2,340,763, 2", 343,703,
No. 2,359,332, No. 2,411,951, No. 2,435,550, No. 2,592,303
No. 2,600,788, No. 2,618,64
No. 1, No. 2,619,419, No. 2,673.8
OJ No. 2,691,659, No. 2,803,
No. 554, No. 2,829,975, No. 2,866
．． No. 706, No. 2,881,167, No. 2.89
No. 5,826, No. 3,062,653, No. 3,1
No. 27,269, No. 3,214,437, No. 3,
No. 253,924, No. 3,311,476, No. 3
, No. 419,391, No. 3,486,894, No. 3. \519,429, same No. 3', 558.3°1
No. 8, No. 3,617,291, No. 3.68, 5
No. 14, No. 3,705,896, No. 3,725,
No. 067, No. 3,888,680, British Patent No. 72
No. 0,284, No. 737,700, No. 813,8
No. 66, No. 892,886, No. 918゜1211
No. 1,019,117, II 1.042.
No. 832, No. 1,047,612, No. 1,398
, No. 828 and No. 1,398,979,
West German Patent Publication No. 814-996, No. 1,070
,030, Belgian Patent No. 724,427, JP-A-46-60479, JP-A-49-29639, JP-A-49-
No. 111631, No. 49-129538, No. 50-1
No. 3041, No. 50-116471, No. 5G-159
No. 336, No. 51-3232, No. 51-3233,
No. 51-10935, No. 51-16924, No. 51
-20826, 51-26541, 51-30
No. 228, No. 51-36938, No. 51-37230
No. 51-37646, No. 51-39039, No. 51-44927, No. 51-104344, No. 51
- No. 105820, No. 51-108842, No. 51-
No. 112341, No. 51-112342, No. 51-
No. 112343, No. 51-112344, No. 51-
No. 117032, No. 51-126831, No. 52
-31738, 53-912 Crocodile, 53-3512
No. 2, No. 53-75930, No. 53-86214,
It is described in the respective publications such as No. 53-125835, No. 53-123129, and No. 54-56429.

A typical coupler that forms a coupling product having a maximum spectral absorption wavelength in the wavelength range from 600 nm to 750 nm is known in the industry as a cyan coupler, and is disclosed in U.S. Pat. No. 2,306,410.
No. 2,356,475, No. 2゜362.5
No. 98, No. 2.367, No. 531, No. 2.369
．． No. 929, No. 2,423,730, No. 2゜4
No. 74.293, No. 2,476.008, No. 2498.466, No. 2,545,687,
Same No. 2゜728.660, Same No. 2.772.162
No. 2゜895.826, No. 2,976.1
No. 46, same side No. 002.836, same side No. 3,419,
No. 390, No. 3446.622, No. 3,47
No. 6.563, No. 3737.316, No. 3,
758,308, British Patent No. 3゜839.044, British Patent No. 478,991, British Patent No. -945,542, British Patent No. 1,084,480, British Patent No. 1゜377.233, British Patent No. No. 1,388,024 and No. 1.543,04
Each specification of No. 0, along with Kli Kaisho 47-37425,
No. 50-10135, No. 50-25228, No. 50
-112038, 50-117422, 50-
No. 130441, No. 51-6551, No. 51-376
No. 47, No. 51-52828, No. 51-108, 84
Spectral absorption in the 0 wavelength range from 7002111 to 850nrm as described in the following publications: Couplers that form a coupling product having a maximum wavelength include JP-B No. 52-24849 and JP-A No. 53-1258.
No. 36, No. 53-129036, No. 55-21094
No. 55-21.095, No. 55-21096, etc.

The silver halide photographic emulsion according to the present invention is so-called
A particularly preferred yellow coupler, which is commonly used with -couplers, is the α-pipap ylacetanilide thread yellow coupler. The silver halide emulsion of the present invention can also be used in combination with a so-called magenta coupler, and a particularly preferred 5-pyrazolone magenta coupler manufactured by Magenta Coupler Co., Ltd. is preferred. No matter which coupler is used in combination, it can be incorporated to improve storage stability and coating solution stagnation. Although various known methods can be used for dispersing these, for example, a method of dissolving these Kabutsu in a high boiling point solvent that is substantially insoluble in water and dispersing it in a woody colloid is preferably used. Particularly useful high-boiling solvents in this case include N-n-butylacetanilide, diethyl lautumide, dibutyl lauramide, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, U-dodecylpyrrolidone. . In addition, in order to promote dissolution of the coupler in this case, a low boiling point solvent or an organic solvent that is easily soluble in water can be used. Examples of these organic solvents include ethyl acetate, methyl acetate, cyclohexanone, acetone, Methanol, ethanol, tetrahydrofurano, 2-methaneol, dimethylformamide, etc. can be used. These organic solvents can be removed by washing with water, coating and drying, or the like.

Furthermore, the silver halide emulsion according to the present invention may contain various other photographic additives, such as known hardeners, spreading agents, and ultraviolet IIFI.
It can contain a k-absorbing agent, a fluorescent whitening agent, a physical property improver (l [full bloom, polymer water dispersion moiety), a combination of phenols and formalin, etc.

Further, the silver halide emulsion according to the present invention is coated on a conventionally known suitable support and dried to produce a silver herignide photographic light-sensitive material. Films such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, etc. or e.g. paper and polyolefin (
A laminated film of two or more types of materials, such as a laminate with polyethylene, polypropylene, etc., is used.

Even though this support has been subjected to various surface improvement treatments to improve its adhesion to the silver halide emulsion,
good. For example, those subjected to surface treatment such as electron impact treatment S or subbing treatment to provide a subbing layer are used.

In order to coat and dry the silver halide photographic emulsion on this support, it is coated by a commonly known coating method such as dip coating, sea-chie coating, bead coating, curtain pad coating, etc., and then dried. be done.

A photographic material comprising a silver halide emulsion according to the present invention is basically constructed as described above, but is further spectrally sensitized to other wavelength regions, that is, am-photon and red. Photosensitivity/%Q Silver Genide Photographic Emulsion Layer, Intermediate Layer, Protective Layer,
The structure may be a combination of various photographic component layers selected from among a filter layer, anti-scratch layer, and backing layer as required.

After exposing a photosensitive material comprising the silver halide photographic emulsion of the present invention, various photographic processing methods are used for development. Processing temperature and time are set according to welfare, and the temperature is at room temperature or lower than room temperature, for example, 1:8℃ or less,
Alternatively, a method in which the temperature is higher than room temperature, exceeding 30°C, for example, around 40°C, or even exceeding 50''C, is preferably used.

In the case of color development processing, as a coloring am main agent, example tGfw
, *-dimethyl-p-phenylenediamine, w,w-diethyl-p-phenylenediacene, -carbaltomethyl-V-methyl-p-phenylenediamine, y-carbaltomethyl-V-tetrahydrofurfuryl-2-methyl -p-phenylenediacene, V-ethyl-V-carboxymethyl-2-methyl-11-phenylenediacene, docarpamidemethyl-doethyl-2-methyl-p-phenylenediamine, V-ethyldotetrahydride Tetrafurfuryl-2-methyl-p-aminophenol, 3-acetylamino-4-adenodimethylaniline, V-ethyl-β-methanesulfonadoethyl-4-aminoaniline, d-ethyl-β- Methanesulfonamidoethyl-3-methyl-4-aminoaniline, the sodium salt of di-methylhydrocarbonate-β-sulfoethyl-p-phenylenediacene, etc. can be used. 1 consisting of the silver halognide photographic emulsion of the present invention True photosensitive materials contain these color-forming agents in the hydrophilic colloid layer as the color-developing agent itself, and certain herbal drug precursors are compounds that can be formed as color-developing agents under alkaline conditions, and aromatic aldehyde derivatives. Examples include Schiff base precursor precursors, polyvalent metal ion complex precursors, phthalate derivative precursors, phosphoric acid amide derivative precursors, sugar amine reactant precursors, and urethane lid precursors.
Precursors for color developing agents are described, for example, in U.S. Pat. No. 3,342.599 and U.S. Pat.
No. 4, No. 2,695,234, No. 3,719,4
92'', British Patent No. 803,783, Japanese Patent Application Publication No. 1983
-185628, No. 54-79035, and Research Disclosure #51°'' No. 5159, No. 12146, and No. 13924.

These aromatic primary amine coloring agents or their precursors need to be added in such amounts that sufficient coloring can be obtained upon activation. This amount varies depending on the type of photosensitive material, etc., but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color-forming agents or their precursors can be used alone or in combination. When incorporated into photosensitive materials, they can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc. It can be added as an emulsified dispersion, or it can be added by impregnating it into a latex polymer as described in Research Disk P-Jar No. 14850. The bleaching and fixing treatments after development are as follows: Bleaching treatment and fixing treatment AV may be performed simultaneously. Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (av), cobal (m), and copper (if), and especially complex salts of these polyvalent metal cations and organic acids, such as ethylene chloride. -tetraacetic acid, nitrilotriacetic acid, v-hydroxyethylethylenecyanodiacetic acid? Aminopolycarboxylic acids, malonic acid, tartaric acid, malic acid, diglycolic acid, metal complex salts such as dithioglycolic acid, ferricyanates, dichromate, and the like may be used alone or in appropriate combinations.

The silver halide photographic emulsion according to the present invention can also be used in so-called black-and-white photographic light-sensitive materials.
Aminophenol-4-aminophenol hydrochloride, M*M-diethyl-
4-aminophenols, represented by 4-aminophenol hydrochloride, 4-aminophenol sulfate, etc.
-Phenyl-3-pyrazolidone, 4,4-dimethyl-1
-3-pyrazolidones such as phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone, hydroquinone, 2-methylhydroquinone, 2 -7 Rehydroxybenzene fRs p 'enylenediami'11 It
'J[, M* p-phenylenediamines such as w-diethyl-p-phenylenediacene sulfate, ascorbic acid, l'-(p-hydroxyphenyl)glycine, etc. may be used alone or in an appropriate combination. can.

Preferred embodiments IIIAIII8A of the present invention are listed below.

1. Claims 10 Negative Lid, characterized in that the color is sensitized with at least one sensitizing dye represented by the general formula tVi and at least one sensitizing dye represented by the general formula B Silver halide photographic emulsion, general formula tvi, where tvi represents the atomic group necessary to form a benzothiazole nucleus, a benzoselenazole nucleus, a naphthothiazole nucleus or a naphthothiazole nucleus. Further, Y represents a sulfur atom or a selenium atom. In addition, R11 and ~ each represent an alkyl group, an alkenyl group, or an aryl group, R1a represents a hydrogen atom, a methyl group, or an ethyl group.
represents.

General formula [vD where 1. #'i% represents an oxygen atom, a sulfur atom or a selenium atom, R21 and - are each an alkyl group,
Table 4: Alkenyl or aryl groups.

2. A negative-working silver halide photographic emulsion characterized by having a benzothiazole nucleus or a benzoselenazole nucleus of the general formula (III) in the combination embodiment 1.

3. Claims characterized in that the color is sensitized with at least one sensitizing dye represented by the following general formula (W) and at least one sensitizing dye represented by the following general formula (VIA') Negative-working silver halide photographic emulsion as described.

General formula [l Here, z14 and - each represent a naphthothiazole nucleus or a toselenazole nucleus.

Also. and ~ represent an alkyl group, an alkenyl group, or an extended aryl group, respectively, ~ represents a hydrogen atom, a methyl group, or an ethyl group, a pair represents an ion removed, and I represents 0 or 1v〇General Formula αd Here, "horse" represents an oxygen atom, a sulfur atom or a selenium atom, and "R" and "Rr" represent an alkyl group, an alkenyl group or an aryl group, respectively.

4. A silver halide color photographic light-sensitive material as claimed in the claims, characterized in that it is color sensitized with a sensitizing color represented by the general formula (1) and the general formula (1) to 10:1.

A negative-working silver halide photographic emulsion as claimed in the claims containing a yellow-forming coupler.

6. A blue-sensitive emulsion layer consisting of the silver halide photographic emulsion described in 5.
A color photographic material having a green-sensitive emulsion layer containing a magenta-forming coupler and a red-sensitive emulsion layer containing a cyan-forming coupler.

7. A color photographic material comprising a negative-lid silver halide emulsion as claimed in the claims, characterized in that it contains a yellow-forming coupler.

Example 1 A silver iodobromide emulsion containing 7 mol of silver iodide and having an average grain size of 0.70 m was sensitized with gold and sulfur in a conventional manner and subjected to vIG separation. Next, a sensitizing dye (1-
6) and (II-6) 1, individually or in combination, and after thorough stirring, stabilizer (stabilizer below - total of 11 sensitizing dyes added per mole of silver chloride) The amount added is 3.0X10' = 2.511/wl, gelatin 5
．． The conditions were adjusted so that 017ze was applied, and the coating and drying were performed. It was exposed to light using an 87-inch scale (manufactured by Konishiroku Photo Industry Co., Ltd.) and developed for 10 minutes at 20° C. using the following developer. After development, it was stopped, fixed, washed with water, and then dried.

The results are shown in Table 1. Each sensitivity in the table is expressed with the sensitivity of Sample 1 as 100.

1 (stabilizer-1) = 4-hydroxy-6-methyl-1
,3,3a,7-chitrazaindene** Composition of the liquid Table 1 As is clear from Table 1, the sensitizing dyes (1-6) and (n
By using -6) alone, approximately twice the sensitivity can be obtained, but by using both together, even higher sensitivity can be obtained. Addition ratio Fi(I-6)! (II-6)=
A ratio of 1:2 to 2:1 is particularly preferable since sensitivity is particularly high.

Furthermore, even in the case of (1-6): (n-6)=l:5, for example, the sensitivity is about 20% higher than the expected average value from an example of using both alone.

Example 2 Next, in order to determine how much increase in sensitivity can be expected when sensitizing dyes are used alone, sensitizing dyes (1-6) and (If-6) were used alone. A blue-sensitive emulsion coating sample was prepared using the same method as in Example 1 except that the amount of addition was changed and the other conditions were the same as in Example 1.
Exposure and development were carried out in exactly the same manner as above. The results are shown in Table 2. Sensitivity is expressed as specific sensitivity with sample 14 set as 100.

Table 2 In so-called 11-plane latent image emulsions, as the amount of sensitizing dye added increases, there is a phenomenon in which sensitivity decreases rapidly beyond a certain amount. It can be seen that there is an optimum amount of sensitizing dye added. From Table 2, sensitizing dyes (f-6), (II-6)
It can be seen that the optimum addition amount is 3.0×1 G-'7 g/mol of silver halide. However, as can be seen from Table 1, when used alone, the sensitivity cannot be exceeded by the combination of sensitizing dyes according to the present invention.

Example 3 A coating solution for a blue-sensitive emulsion layer was prepared in the same manner as in Example 1. The sensitizing dyes used are shown in Table 3.

Immediately after preparing this coating solution, it was left to stand at 43° C. for 3 hours and then for 6 hours before coating to produce coated samples. The exposure and development conditions were the same as in Example 1, and the results obtained were used in Example 3.
Shown in the table. Sensitivity of samples coated immediately after preparation of coating solution for each coating Table 3 shows the behavior of this emulsion in the case of no dye (sample 22), with a relatively small change in sensitivity and a tendency for capri to gradually increase. I understand that. Comparison of samples such as sample n and sample 23.24 shows that those containing sensitizing dyes show a decrease in sensitivity over time, and a tendency to be large in the early stages is observed. In addition, when comparing sample 23.24.26.27 with sample 25.28.29.30, which is a combination of sensitizing dyes according to the present invention, when used alone, desensitization was observed over time, and an increase in capri. In contrast, when used in combination, the increase in sensitivity and capri was strongly suppressed.

Example 4 Silver iodobromide emulsion containing 5 mol% silver iodide (average grain size 1
μm) was sensitized with gold and sulfur according to a conventional method, divided into 16 parts, sensitizing dyes were added alone or in combination, stirred for 5 minutes, and then a stabilizer (stabilizer-1) was added to the halogen It was added in an amount of 1 liter per mole of silveride. In addition, 0.3 mole of Y-4-coupler (Y
(7-1) was added as a dispersion emulsified with digtylphthalate (hereinafter abbreviated as DBP), and this coating solution was applied immediately after preparation, after being left at 43°C for 3 hours, and after being left for 6 hours, to prepare samples. . Coating was carried out on cellulose triacetate Lyle's surface so that the amount of silver coated was 1 jF/ce as metallic silver and the amount of iratin was 4 f/wl, and then 19/I gelatin was coated as a protective layer. did. This sample was exposed as in Example 1 and processed according to the following processing steps.

O-1 α-(4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-)riazolidinyl)]-]α-bivalyl-2-chloro5-7-(2,4- Di-t-amylphenoxy) butanate] acetanilide treatment process (treatment time) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds with water Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds with water Washing and drying for 3 minutes and 15 seconds.Color developing solution composition: 4-azino-3-methyl-bi-ethyl-y-(β- and droxyethyl) aniline sulfate 4.8 g Anhydrous sodium sulfite 0.14 g Hydroxyanidine monosulfate L9811 sulfate @
0.74 Anhydrous Potassium 28.85 F Anhydrous Potassium Bicarbonate 3.469 Anhydrous Potassium Sulfite 5.10 F Potassium Bromide
1.165' Sodium Chloride
0.14 trilotriacetic acid trisodium salt (l hydrate) 1.20 jl potassium hydroxide
1.481 Add water to make up to 1 liter.

Bleach composition Iron diamine tetraacetate Al
1 Ethylenecyadentetraacetic acid 2 ammonium salt 10
．． OII ammonium bromide 150. [
'Add glacial acetic acid lαOd water to make 1j, and adjust to pH 6.0 using ammonia water.

Fixer Composition Thiosulfur Ammonium 17LOj Anhydrous Sodium Sulfite 8.6I Sodium Metasulfite 2.31 Add water to make it 11, and use vinegar 1I11 to pH = 6. OK Adjust.

Stabilizing liquid composition: Formalin (37% aqueous solution) Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add water to make 11.

After drying, the transmission density of the dye image formed on each sample was measured using Sakura Densitometer PD Mu-60 (manufactured by Konishiroku Photo Industries) V and an attached blue filter.

The results are shown in Table 4. The sensitivity immediately after preparing the coating solution is that of sample 3.
The specific sensitivity was expressed as 21t100. After 3 hours and after 6 hours, the specific sensitivities of the emulsions coated immediately after each preparation were expressed as 100.Table 4 shows that the behavior of this emulsion was determined from the case of no dye, etc. It can be seen that the change in sensitivity is relatively small, and the capri tends to gradually increase. Although the decrease in sensitivity increases with time after preparation of the coating solution in those containing a sensitizing dye, the degree of decrease is greater than in the case without a coupler shown in solid line example 3, and the decrease is particularly large at the initial stage. According to Table 4,
It has been confirmed that high sensitivity can be obtained by the combination of sensitizing dyes according to the present invention, and changes in sensitivity and capri when the coating solution is left at high temperatures are suppressed in photographic systems using color flow sources. . Thus, it will be easily understood that the present invention exhibits excellent effects even in photographic systems using couplers.

Solid Line Example 5 A silver chlorobromide emulsion containing 15 ml of silver chloride with an average grain size of 0.7 μm was chemically thermally formed using I×10 mol of sodium thiosulfate per 1 mol of silver halide according to a conventional method. After dividing this, the sensitizing dyes shown in Table 4 were added alone or in combination, and after stirring for 5 minutes, stable
A stabilizer (stabilizer-1) was added in an amount of lIi per mole of silver halide. Further, 0.3 mole of yellow coupler (dispersed) was added per mole of silver halide.The coating solution thus prepared was left at 43°C for 3 hours immediately after preparation, and then coated after being left for 6 hours. , Anatase ■On a photo paper support coated with polyethylene containing titanium oxide, the amount of silver per coating is 0.35 jl/j as metallic silver.
.

The amount of gelatin was 3.01/wl, and gelatin was coated thereon as a protective layer at a rate of 2.01/d. The protective layer contained bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a hardening agent.

The samples thus prepared were exposed to a light wedge in the same manner as in Solid Line Example 1, and then the following processing steps (process mv) were carried out. -6011 (manufactured by Konishiroku Photo Industry Co., Ltd.) and the attached blue filter.

(τa-2)α-(l-benzyl-2,4-dioxo-
3-ynodazolidinyl)-α-pivalyl-2-chloro5-Cr-(2,4-di-t-amylphenoxy)butanamide]acetanilide (color stain inhibitor-1) 2.5-di-t-octylhide p quinone Here, as in Example 4, high sensitivity can be obtained by the combination of the sensitizing dyes according to the present invention, and changes in sensitivity and fog when the coating solution is left at high temperatures are suppressed, according to JI.
I got a B.

Processing process Color development 33℃ 3 minutes 30 seconds Starch fixation 3
Wash with water for 1 minute and 30 seconds at 3℃ 30-34℃
3 revolution Dry color developer composition Pure water 8
0〇-Ethylene glycol 15 m
Benzyl alcohol 18 11j Hydroxylamine sulfate 2.0 F Anhydrous potassium carbonate 30.0jl Potassium bromide 0.5# Sodium chloride
1.5v anhydrous potassium sulfite
2. O2'-ethyl-y-β-methanesulfonamidoethyl-3-methyl-4-anonoaniline sulfur 11' [451 Add pure water to 11 and adjust to pli = 10.2 with potassium hydroxide or sulfuric acid. .

- Bleach-fix solution composition Pure water
750 11j Sodium Sodium Tetraacetate
50 1,000 ammonium sulfate
85 1 Sodium bisulfite 10
1 Sodium metabisulfite 2I Sodium ethylenediaminetetraacetic acid [20g sodium bromide\3. ON pure water plus 11
and adjust the pH to 7.0 with aqueous ammonia or sulfuric acid.

Example 6 A photographic paper support covered with a polyethylene film containing anatase titanium oxide was subjected to corona discharge machining. The amount of 1 is expressed as the amount per liter of photosensitive material, and the amount of 71p silver genide is expressed in terms of silver. Ta.

Layer 1: 0.45N blue-sensitive silver chlorobromide emulsion (average grain size 0.70
1.47N gelatin and 0.8N yellow coupler (yo-2) and
．． Color stain inhibitor of 0151 (color stain inhibitor-1) t-Blue-sensitive emulsion layer 2 containing dissolved DBP of 0,41! 1.03N gelatin, 0.015jl color stain preventive agent (color stain preventive agent-1) t-dissolved 0.03jl DI
First intermediate layer 3 containing IP: 0.40F green-sensitive silver chlorobromide emulsion (average grain size 0.45
μ■, containing more than 20 moles of silver chloride) 1.85F gelatin and 0.6351 magenta coupler (MO-1 below)
, o, osII of 5,5-dimethyl-1,3-cyclohexa/dione (hereinafter abbreviated as DMQH) and 0.0151
10 color stain preventive agent (color stain preventive agent-1) dissolved in 0,
Ijj! containing 341 tricresyl phosphate (hereinafter abbreviated as TOP). Photosensitive emulsion layer MO-1: 3-(2-chloro-5-(1-octadecenylsuccinimide)anilino)-1-(2,4,6-)lichlorophenyl)-5-pyrazolone layer 4: 1 .4551 gelatin, 0.2g ultraviolet absorber (
UV-1 below), 0.3I UV-IIg & astringent (0 below)
7-2) and a second intermediate layer UV-112-(2-hydroxy-3,5- di-tert-butylphenyl)-benzotriazole υV-2+2-(2-hyroxy-5-t-butylphenyl)-benzotriazole layer 5: 0.30 jl of red-sensitive silver chlorobromide emulsion (average grain size 0.
40 μm, containing 20 moles of silver chloride), 1.61 gelatin array KO, 421 cyan coupler (O〇-1 below)
, 0.05F of I) Molt and 0.3I of D in which Molt and 0.005F of color stain preventive agent (color stain preventive agent-1) are dissolved.
Red-sensitive emulsion layer containing BP ao-1+ 2-(2-(14-di-t-amylphenoxy)butanami)'J-4,6-seek00-5-methylphenol layer containing 61 181 gelatin A silver hemoglobin emulsion using the protective layer surface layer IK was prepared as follows. IX per mole of silver halide emulsion
Addition of 'IO-' mole of sodium thiosulfate, chemical ripening! The sensitizing dye was added as a 0.1% solution prepared in advance 5 minutes before the end of the chemical ripening. 5 minutes later,
At the end of chemical ripening, stabilizer (stabilizer-1) Iko,
It was added as a s% aqueous solution. After the addition, a 10% aqueous gelatin solution was added, stirred, and then cooled to set.

The silver halide emulsion used in layer 3 was chemically sensitized using 1.5 x 10-' moles of sodium thiosulfate per mole of silver decagenide, and 3. OX10 mol of anhydro-5,5'-diphenyl-9,-ethyl-3
The silver halide emulsion used in layer 5 was prepared in the same manner as the emulsion in layer 1, except that easy (r-sulfopropyl)oxacarbonanine human tetraoxide was used. It was prepared in the same manner as the layer 3 emulsion, except that .0x10-' moles of 3.3'=di(β-dihydroxyethyl)thiadicarbocyanine bromide was used as the sensitizer.

In addition to the above materials, Bi1. (vinylsulfonylmethyl)ether and 11i cloth 11fJIJ to 1 mole of AgX. The type and ratio of pigments and blue sensitivity are the 5th I! It was shown to. Sensitivity is sample 47
It is expressed as a specific sensitivity with 100.

Table 5 The above four types of samples were exposed to light through a color negative, printed,
When the same process as described in Example 4 was performed, the present invention
48.49.5G using a combination of sensitizing dyes according to id
4.Good color reproduction, no different from the conventional printed photosensitive material 47,
A color print showing tone reproduction was obtained. Further, when the sensitivity of the yellow dye image was determined by light simulated exposure, it was found that the sensitivity was high as shown in Table 5.

Procedural amendment! , Indication of the case Patent Application No. 190407 of 1982 2 Name of the invention Silver hagenide, true emulsion 3 Relationship with the case of the Ministry making the amendment Patent applicant Address 1-26 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 2 Name (127) Konishiroku Photo Industry Co., Ltd. Address 1-6 Sakura-cho, Hino-shi, Tokyo, “Claims” column and “Detailed description of the invention” column 7 of the specification subject to amendment , Contents of the amendment (1) The scope of the claims will be amended as shown in the attached sheet.

C) The detailed description of the invention is amended as follows.

2. Scope of Claims Negative lidded chain true emulsion containing a combination of a sensitizing dye represented by the following general formula CI) and a sensitizing dye represented by the following general formula 〇 General formula CI) Here zll and 2+1 are benzimidazo-
Atomic groups necessary to form vLT in the following forms: 1, 1, 2, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3 represents.

Also, R3, and RI! represents an alkyl group, an alkenyl group, or an aryl group, respectively, and %fL+s represents a hydrogen atom, a methyl group, or an ethyl group.
represents an anion, and j represents O or 1.

General formula (n) where & is a benzoxazole nucleus, 7) odorazole, benzothiazole, naphthothiazole, benzodiazole, natuto nazole, benzimidazole, or natutoimidazole. Represents the atomic group necessary to form a cell. Also, 2.
Represents the atomic group necessary to express 2-thioshilenasiri 2-λ4-dione, and -1 and ~ represent an alkyl group, alkenyl 1
kai or a, the reel group is represented.

Procedural amendment sound I, indication of the case Patent application No. 190407, filed in 1982, 2. Four-gen photosensitive emulsion 3 to the title of the invention.Relationship with the case of the person making the supplement.Patent applicant address: 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo 'J-26 No. 2 Name (+27) Konishiroku Photo Industry Co., Ltd.? 1 Representative Director Nobuhiko Moto 4, Agent 191 Address 11R Sakura-cho, Hino-shi, Tokyo Konishi Roku Shasei 1-Gyo Co., Ltd. Spontaneous & Amendment Subject of the Specification, ``Claim 41 of Patent Claims'' and "Detailed Description of the Invention" Column 7, Contents of Amendment (1) The scope of claims is amended as shown in the attached sheet.

(2) The detailed description of the invention is amended as follows.

(Ill Paper) 2. Claims A sensitizing dye represented by the following general formula (I) and the following 3 general formulas (
A negative halogenated photographic emulsion containing a combination of a sensitizing dye represented by If).

General formula CI) rxf3)i where Zll and zlfi are Sorebe/Dioxazole, (4 Tei, Miss Natsutoushi, Miss Benzothiazole, Miss Natsutothiazole, Miss Benzoselenazole, Miss Natsuto and Miss Nazor) , pe/ciimidazole (7), pyridine (S) or quinoline (V). In the expression, island represents a hydrogen atom, a methyl group, or an ethyl group.Furthermore, ka represents an anion, and %1 represents .01!411.

General formula (n) Here, z is Miss Benzoxazole, Miss Naphthoxazole, Miss Benzothiazole, Miss Natsutothiazole, Benzo Shichishi Nazole 幀, Natsuto Shichishi Nazor Tei, Be/Shiiden Dazole@t or Natsutto. The two days we met represent the atomic groups necessary to form Miss Imidazole,
Represents the atomic group necessary to form 2-thiohydantoin or 2-thionazolidine-λ4-dione, and 〈〉 and 〈〉 represent an alkyl radical, an alkenyl radical, or an aryl group, respectively.

Claims (1)

[Claims] A sensitizing dye represented by the following general formula (1) and the following general formula [I
A negative type silver oxide photographic emulsion containing a combination of a sensitizing dye represented by D. General formula (I) where 4 and 2. are the benzoxazole nucleus and
Nattuoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus,
Represents the atomic group necessary to form a pyridine nucleus or quinoline nucleus. Further, R11 and R each represent an alkyl group, an alkenyl group, or an alkyl group, and H and R represent a hydrogen atom, a methyl group, or an ethyl group. moreover ,?
represents an anion, and 1 represents 0 or 1v. General formula [button here 4. is the atomic group necessary to form a benzoxazole nucleus, a natuoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzonazole nucleus, a naphthoselenazole nucleus, a benzimidazole nucleus, or a toimidazole nucleus. The stone also represents the rhodanine nucleus,
2-Thiovidantoin core or 2-thioselenazoline-
The atomic groups necessary to form a 2,4-dione nucleus, ``a'', and ``e'' represent an alkyl group, an alkenyl group, or an aryl group.