JPH0635103A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material having high sensitivity to light in the specified wavelength region of semiconductor laser beams and the like but low sensitivity to light in the other wavelength regions and the sensitivity small in change during its storage. CONSTITUTION:The silver halide photographic sensitive material is spectrally sensitized by a sensitizing dye having a polarographic half-wave reduction potential baser than -1.25V vs SCE (saturated calomel electrode) and a polarographic half-wave oxidation potential nobler than 0.38V vs SCE, and it is spectrally sensitized in the infrared wavelength region in the J-band type so as to have a spectrally sensitized sensitivity maximum in the wavelength region of >=730nm and as high as >=4.5 times the sensitivity in the wavelength longer by 30nm than this maximum sensitivity wavelength and as high as >=2 times that of this wavelength, and it contains a photographic useful reagent precursor.

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 which is spectrally sensitized in the infrared region. The present invention relates to a silver halide photographic light-sensitive material which is sensitized to a so-called J-band type having low sensitivity in the wavelength range and has improved storage stability.

[0002]

2. Description of the Related Art One of the exposure methods for a photographic light-sensitive material is to scan an original image and expose the silver halide photographic light-sensitive material on the basis of the image signal to expose a negative or positive image corresponding to the image of the original image. There is known an image forming method by a so-called scanner method for forming an image. There are various recording apparatuses that have practically used the image forming method based on the scanner method, and the recording light source of the recording apparatus based on these scanner methods has been conventionally used.
Glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, etc. have been used. However, each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these drawbacks, Ne-He laser, argon laser, He
There is a scanner that uses a coherent laser light source such as a Cd laser as a light source of a scanner system. Although they can obtain high output, they are large in size, expensive, require a modulator, and use visible light, so that the safelight of the photosensitive material is limited. There are drawbacks such as inferiority. On the other hand, a semiconductor laser is small and inexpensive, is easy to modulate, has a longer life than the above laser, and emits infrared light. Since the safelight can be used, there is an advantage that handling workability is improved. However, since there is no photosensitive material having high photosensitivity only in the infrared region and excellent in storage stability, the characteristics of the semiconductor laser having excellent performance as described above cannot be fully utilized.

As one of the manufacturing techniques for photographic light-sensitive materials, a technique of adding a certain sensitizing dye to a silver halide photographic emulsion to extend its light-sensitive wavelength range to the longer wavelength side,
That is, it is generally well known that the spectral sensitization technique is applied and that the spectral sensitization technique is applied not only in the visible region but also in the infrared region. For spectral sensitization in the infrared region, sensitizing dyes having absorption for infrared light are used, and these are described, for example, in “The Theory of the Photographic Proces” by MeeS.
s, 3rd edition "(issued in 1966 by MacMillan) 198
~ Page 201. In this case, it is desirable that the spectral sensitivity, that is, the sensitivity to light in the desired infrared region, is high, and also during storage of the light-sensitive material and presence of the silver halide emulsion in the liquid during the manufacturing process. It is desirable that the change in sensitivity is small. Therefore, many sensitizing dyes have been developed so far. These are described, for example, in US Pat.
95,854, No. 2,095,856, No. 2,
955,939, 3,482,978, 3,552,974, 3,573,921, and 3,582,344. However, even if the sensitizing dyes described in these are used, it cannot be said that the sensitivity and storability are sufficient.

Further, in the light-sensitive material, the spectral sensitivity is remarkably increased by adding a second kind of a specifically selected organic compound in addition to the spectral sensitizing dye.
The storability may also be improved incidentally, and this effect is well known as a supersensitizing effect. Regarding supersensitization in the infrared region, JP-A-59-191,032 and 59-1.
92,242 and 60-80,841 describe combinations of infrared sensitizing dyes (such as tricarbocyanine dyes and 4-quinoline dicarbocyanine dyes) with cyclic onium salt compounds and certain heterocyclic compounds. For improvement of storability, many patent specifications such as JP-A-1-221,737 describe combinations of infrared sensitizing dyes with certain compounds. However, the techniques described in these have not yet achieved sufficiently high sensitivity.

Since the emission wavelength of laser light including a semiconductor laser is fixed, it is sufficient to strongly sensitize only a specific wavelength that matches the oscillation wavelength of the laser.
It is often preferable that the sensitivity in the wavelength region other than the oscillation wavelength of the laser is as low as possible from the viewpoints of safety of safe light and prevention of color mixture in a multi-layer color photosensitive material.
Such a technique of strongly sensitizing only a specific wavelength is known as J-band sensitization in the spectral sensitization technique of a silver halide photographic emulsion. The J-band is caused by the formation of a special aggregate called J aggregate, which has a very high absorbance and an extremely sharp absorption with a very narrow half width. The spectral sensitivity also shows a sharp spectral sensitivity distribution spectrum reflecting this absorption characteristic. An extremely large number of examples of this J-band sensitization are known in the visible light region. For example, it is an essential and general spectral sensitization method for the production of full-color light-sensitive materials. There are very few examples in the light region, AH Herz, Photogr. Sci. Eng., 18
Volume (3), pages 323-335 (1974), and H. Kamp.
fer, ICPS Proceedings pp. 366-369 (1986), only a simple description is seen, and an example in the coexistence of a color coupler is not known. On the other hand, in an infrared sensitizing system having a sensitizing maximum on the wavelength side longer than 730 nm, desensitization strongly occurs when the amount of the sensitizing dye added is increased (US Pat. No. 4,011).
No. 1,083). This desensitization is well known as the intrinsic desensitization caused by the sensitizing dye, and it is also known that the dye having a longer wavelength absorption becomes larger. In the infrared sensitizing dyes as described above, this desensitization is extremely large, and therefore the coverage of the sensitizing dye on the surface of the silver halide grain is usually unavoidably limited to about 10 to 20%. The light trapping rate is low, and the obtained spectral sensitivity is extremely low as compared with the spectral sensitivity applied in the visible region, and the storage stability becomes poor. The spectral sensitivity distribution obtained in this state was very broad due to the absorption in the molecular state. Furthermore, although the above-mentioned document mentions the formation of the J-band, it is said that a very broad spectral sensitivity distribution spectrum was obtained with a silver chlorobromide emulsion mainly composed of silver iodobromide and silver bromide. From this, it is assumed that the spectral sensitization is a mixture of M-band type spectral sensitization based on the molecule of the sensitizing dye in the molecular state and J-band type spectral sensitization based on the J-aggregate of the sensitizing dye. , I did not have enough awareness to handle it under laser exposure or under safelight and to adapt it to full-color light-sensitive materials, so there is a lack of recognition to suppress the sensitivity in unnecessary areas.
-Although band sensitization was obtained, J with a narrow spectral sensitization distribution
-It is not the one that mainly realized band-type spectral sensitization,
It was extremely insufficient from the viewpoint of practicality.

Therefore, there is a demand for a sensitizing method that provides J-band sensitization having a high spectral sensitivity adapted to the wavelength of the semiconductor laser light, and that has a low sensitivity in an unnecessary region in the infrared region. Further, when the spectral sensitization having a wavelength longer than 730 nm is attempted, the spectral sensitizing dye used becomes a dye capable of efficiently absorbing light having a long wavelength. Japanese Patent Laid-Open No. 61-137,149
No. 63-197, 947, No. 55-13, 505.
And the above-mentioned JP-A-59-191,032 and 5
Infrared sensitizing dyes are disclosed in 9-192,242, 60-80,841 and the like, but dyes having a long conjugated methine chain are used in order to have absorption in the infrared region. With such a cyanine dye having a long methine chain, it is extremely difficult to form a J-aggregate on a silver halide grain to predominantly perform J-band sensitization, and the reduction potential is not so base and thus sensitized. It is known that the efficiency is low and the oxidation potential is less than that of the visible dye, so that the stability against wet heat and oxygen is poor. This tendency becomes more remarkable when a color coupler necessary for obtaining a full-color image coexists. In order to produce and provide silver halide light-sensitive materials inexpensively in large quantities and uniformly, it is necessary to add a spectral sensitizing dye and store the spectrally sensitized silver halide emulsion in a solution state for several hours at times. However, the large decrease in the sensitivity of the above-mentioned infrared dye in such a state has been a serious problem in production. Furthermore, a decrease in sensitivity and an increase in fog during the period from manufacturing to use are also serious problems. Commercially available infrared-sensitive silver halide light-sensitive materials, and even black-and-white infrared light-sensitive silver halide light-sensitive materials that do not coexist with color couplers, have to be stored in a refrigerator or freezer until they are used. There are things that can't be kept, and improvements are eagerly awaited. On the other hand, the speed of processing using an automatic processor has been increasing in recent years. Fogging is likely to occur due to the high temperature development accompanying it, and further, a sufficient time for decolorization is not secured due to the short-time processing, and residual color due to the sensitizing dye is becoming conspicuous. Overcoming light-sensitive materials are desired.

[0007]

An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity to infrared light, and to have high spectral sensitivity in a desired wavelength range. However, the sensitivity of unnecessary wavelength range was suppressed,
In particular, it is an object of the present invention to provide an improved silver halide photographic light-sensitive material capable of rapid processing, which has high sensitivity to semiconductor laser light and has sufficiently low sensitivity to light other than semiconductor laser light. The second purpose is to enable ultra-rapid processing in which the emulsion is stored in a solution state before coating and the photographic sensitivity in the infrared region of the light-sensitive material during storage after coating is lowered and the increase in fog density is suppressed. Another object is to provide a novel silver halide photographic light-sensitive material.

[0008]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having a support and at least one silver halide photographic emulsion layer, and at least one of the silver halide emulsion layers. The layer has a polarographic half-wave reduction potential less than -1.25 V for a saturated calomel electrode,
The polarographic half-wave oxidation potential contains a silver halide emulsion spectrally sensitized with at least one spectral sensitizer having a noble potential of more than 0.38 V, and the silver halide emulsion layer comprises 73
It has a sensitization maximum at a wavelength longer than 0 nm, and the sensitivity at this spectral sensitivity maximum wavelength by the spectral sensitizer is 4.5 times or more of the spectral sensitivity for light having a wavelength 30 nm longer than the spectral sensitivity maximum wavelength, The spectral sensitivity is spectrally sensitized to be twice or more of the spectral sensitivity to light having a wavelength shorter than 30 nm by the maximum wavelength and is photographically useful in at least one of the emulsion layer and / or other hydrophilic colloid layer. It has been achieved by using a silver halide light-sensitive material characterized by containing at least one precursor of a reagent. The spectral sensitivity distribution spectrum of a silver halide photographic emulsion does not completely correspond one-to-one with the absorption of the sensitizing dye used for spectral sensitization on silver halide, but it reflects it. .
Therefore, the silver halide emulsion layer has the maximum sensitization at a wavelength longer than 730 nm, and the light absorption by the spectral sensitizer satisfies both the following formulas (1) and (2). Spectral sensitization is essential for achieving the object of the present invention. Abs (peak wavelength) / Abs (peak wavelength +30 nm) ≧ 4.5 (1) Abs (peak wavelength) / Abs (peak wavelength -30 nm) ≧ 2 (2)

However, if the spectral sensitizing dye is simply added to the silver halide emulsion, it has a maximum sensitization at a wavelength longer than 730 nm and satisfies the above-mentioned spectral sensitivity ratio and / or optical density ratio. It is difficult to do so, and 6.2 × 10 ⁻⁷ mol per 1 m ² of surface area of silver halide grains (this amount means that when the occupied area per molecule of sensitizing dye is 106 Å ² , the added sensitizing dye is If all of them are adsorbed in a single layer on silver halide grains, the amount corresponds to the amount covering about 40% or less of the grain surface) or more and 2.7 × 10 ⁻⁶ mol or less, and more preferably 9.3 × 10 ^−7. Molar or more 2.1 × 10 ^-6
Mol or less, more preferably 1.1 × 10 ⁻⁶ mol or more and 1.9 × 10 ⁻⁶ mol or less, 40 ° C. or more and 90 ° C. or less, more preferably 50 ° C. or more and 75 ° C. or less, and further preferably 55 ° C. It was possible to satisfy the above-mentioned sensitivity ratio and / or optical density ratio by adding and aging in the range of 1 to 65 ° C.

Whether or not the above-mentioned sensitivity ratio is satisfied is determined by exposing a coating film having a silver halide emulsion layer to which a spectral sensitizing dye is added through a wedge with an isoenergy spectral exposure machine, and then developing and exposing each film. Compare the sensitivities at the wavelengths. The sensitivity is the reciprocal of the exposure amount when the black-and-white development is performed to give a density obtained by adding 0.2 to the fog density, and when the color development is performed, the density is obtained by adding 0.5 to the fog density. It was expressed as the reciprocal of the exposure dose. When the color coupler does not coexist, the development process may be performed by developing with an appropriate black-and-white developing solution such as D-72, stopping and fixing, and then washing with water. Further, the development process in the case where a coupler is coexistent may be performed with an appropriate color developing solution. An example of the color development process performed is shown below. [Processing process] [Temperature] [Time] [Replenishment amount] ^* [Tank capacity] Color development 35 ℃ 45 seconds 161 ml 17 liters Bleach fixing 30 to 35 ℃ 45 seconds 215 ml 17 liters Rinse 30 to 35 ℃ 20 seconds -10 Liter Rinse 30-35 ° C 20 seconds -10 liters Rinse 30-35 ° C 20 seconds 350 ml 10 liters Dry 70-80 ° C 60 seconds (3 tank countercurrent system from rinse to rinse) * Replenishment amount is photosensitive Amount per 1 m ^{2 of} material The composition of each processing solution is as follows. [Color developer] (Tank solution) (Replenisher) Water 800ml 800ml Ethylenediamine-N, N, N-tetramethylenephosphonic acid 1.5g 2.0g Triethanolamine 8.0g 12.0g Sodium chloride 1.4g-Potassium carbonate 25.0g 25.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 5.5 g 7.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd. 1.0g 2.0g Add water 1000ml 1000ml pH (25 ℃) 10.05 10.45 [Bleaching fixer] (same as tank solution and replenisher) Water 800ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water was added to 1000 ml pH (25 ) 6.0 [Rinse solution] (Same as tank solution and replenisher) Ion-exchanged water (calcium and magnesium are 3 ppm or less for each) In addition, the spectral sensitizing dye was added in the same manner to determine whether the above-mentioned absorbance ratio was satisfied. The coating film having a silver halide emulsion layer may be measured with a spectrophotometer equipped with an integrating sphere (for example, spectrophotometer U-3410 manufactured by Hitachi Ltd.). The measurement wavelength range is 30 more than the peak wavelength in the infrared range.
Absorbance at peak wavelength (Ab
s), the absorbance at a wavelength of 30 nm long wavelength from the peak wavelength and the absorbance at a wavelength of 30 nm short wavelength from the peak wavelength are obtained, and their ratio may be obtained according to the above equations (1) and (2). .

The spectral sensitizing dye used in the present invention may be any one as long as it satisfies the above-mentioned sensitivity ratio and / or optical density ratio and has the maximum sensitization at 730 nm or more. One of the objectives is to reduce the photographic sensitivity in the infrared region and increase the fog density of the emulsion, which has high sensitivity and is stored in a solution state before coating and during storage after coating. In order to provide a suppressed silver halide light-sensitive material, the polarographic half-wave reduction potential of the spectral sensitizing dye used for saturated calomel electrode is -1.25.
It is desirable that the polarographic half-wave oxidation potential is nobler than V and is nobler than 0.38 V, and that the above object can be almost achieved by performing J-band sensitization in the infrared region using such a spectral sensitizing dye. The inventors of the present invention previously filed Japanese Patent Application No.
-91,437. The relationship between the polarographic half-wave reduction potential of a spectral sensitizing dye and the spectral sensitization efficiency is, for example, T. Tani, T. Suzumoto, K. Ohzeki, Journal of Phy.
As described in sical Chemistry, Vol. 94 (1990), p. 1298, etc., the lower the half-wave reduction potential, the better the efficiency. However, the half-wave reduction potentials of the sensitizing dyes that bring about the conventional molecular type spectral sensitization, which are described in the above-mentioned infrared sensitizing patents, are -1.1 to 1-1.
Most of -1.25V vs SCE are not so base, and the sensitization efficiency is extremely worse than the dye for visible region sensitization having a more base half-wave reduction potential. As a result of being able to perform infrared sensitization by J band sensitization, the present invention makes it possible to use a sensitizing dye having a high sensitizing efficiency, which is more base than -1.25 V vs SCE. In order to further increase, it is more desirable that the polarographic half-wave reduction potential of the sensitizing dye used is less than -1.25 V vs SCE. On the other hand, the oxidation potential of the above-mentioned molecular type infrared sensitizing dye that has been used conventionally is 0.40 V vs.
The ones that are more base than SCE are common, and most are 0.35V vs.
It is not uncommon to find pigments that are more base than SCE and 0.30 V vs. SCE. This is considerably less than the sensitizing dye used for the visible region. When the oxidation potential becomes more base,
It becomes more susceptible to oxidation. Therefore, the sensitivity of an infrared-sensitive material spectrally sensitized with a conventional molecular sensitizing dye having such a base oxidation potential is remarkably lowered during storage. It was found that the stability during storage was significantly improved by J band type sensitization with a sensitizing dye having an oxidation potential of 0.38 V vs. SCE. Therefore, if a J-band type sensitization is performed using a sensitizing dye having a polarographic half-wave reduction potential less than -1.25 V vs SCE and a polarographic half-wave reduction potential less than 0.38 V vs SCE, Japanese Patent Application No. In addition to dramatically improving the spectral sensitivity as disclosed in JP-A-91,437, the photographic sensitivity in the infrared region of the emulsion stored before being coated in solution and the light-sensitive material during storage after coating It is also possible to suppress the decrease of the color density and the increase of the fog density. In order to further improve the storage stability of the silver halide emulsion subjected to such spectral sensitization and further suppress the fog associated with high-temperature rapid development, it is possible to prevent fog of a heterocyclic compound having a mercapto group, which is well known from the past. The agent could not be said to be effective. That is, the combined use of the compounds suppressed the fog, hindered the J band sensitization, lowered the sensitivity and suppressed the development. Further, the combination of a conventionally well-known development accelerator with the aim of further improving the rapid processing property brings about an increase in fog during storage, which is never preferable. On the contrary, when at least one precursor of the photographically useful reagent is used in combination, the intended effect is exhibited without inhibiting the J-band sensitization, and the above-mentioned object is achieved more effectively. Polarographic half-wave potential measurements are performed by T. Tani, K. Ohzeki, K. Seki, Journal of the
Electrochemical Society, 138, 1411-14
P. 15 and J. Lenhard, Journal of Imaging Science,
It may be measured by the phase discrimination second harmonic AC voltammetry method described in Volume 30, pages 27 to 35.

The precursor of a photographically useful reagent used in the present invention is a precursor in which a blocking group that impedes the expression of the function of a photographically useful reagent is released at a required timing so that the function of the photographically useful reagent is expressed. Means a compound designed to. The required timing here depends on the function of the photographically useful reagent, and examples thereof include the time after the spectral sensitizing dye is adsorbed on the silver halide grains, or the time of development and fixing in the image forming process.

Typical examples of the photographically useful reagent precursors used in the present invention are described in the following patent specifications and the like. Japanese Patent Publication No. 55-9696, Japanese Patent Publication No. 55-173
69, British Patent 1,402,819, U.S. Patent 3,888,677, U.S. Patent 3,649,267.
Issue No. 3,674,478 Issue No. 3,932,480
No. 3,993,661, JP-B-54-39727
Japanese Patent Publication No. 47-44805, Japanese Patent Laid-Open No. 52-8,8.
28, JP-A-57-82,834, US Pat.
311, 474, 3,615, 617, JP-A-4
9-111,628, U.S. Pat. No. 4,199,354.
Japanese Patent Publication No. 57-22099, Japanese Patent Laid-Open No. 51-63,6.
18, U.S. Pat. No. 3,980,479, French Patent No. 2,282,124, JP-A-50-28823, JP-B-55-34927, and U.S. Pat. No. 4,009,02.
9, JP-A-53-110,827, US Pat. No. 4,
139,379, JP-A-53-110,828, JP-A-54-130927, JP-A-56-55144.
JP-A-56-55454, JP-A-56-1643
42, JP-A-54-145135, U.S. Pat. No. 4,
248,962, JP-A-55-53330, US Pat. No. 4,310,612, JP-A-56-77842.
No. 4, U.S. Pat. No. 4,307,175, West German Publication No. 3,
105,026, British Patent No. 2,072,363,
U.S. Pat. No. 4,330,617, JP-A-57-402
45, JP-A-57-112752, British Patent No. 2,
No. 087,581A, West German publication No. 3,006,268
No. 56-138736, Research Disclosu
Re magazine, December 1981, Item No. 21228, JP-A-57-76541, US Pat. No. 4,335,20.
No. 0, JP-A-57-135949, European Patent No. 005.
6444A2, West German Publication No. 3,008,588, JP-A-56-142530, European Patent 0045129A.
No. 2, JP-A-57-56837, JP-A-57-844.
53, JP-A-57-135944, JP-A-57-1
35945, JP-A-57-136640, and JP-B-5.
6-40818, JP-B-59-33901, JP-B-59-93442, JP-B-60-29937, JP-A-48-42933, JP-A-54-154324,
JP-A-55-59461, JP-A-57-27253
JP-A-59-10540, JP-A-59-6513
7, JP-A-59-105641, JP-A-59-10.
5642, JP-A-59-121328, JP-A-59
-131933, JP-A-59-135463, JP-A-59-180557, and JP-A-59-197037.
JP-A-59-198453, JP-A-59-201
057, JP-A-59-202459, JP-A-59-
206836, JP-A-59-210440, JP-A-59-218439, JP-A-59-219741,
JP-A-60-17440, JP-A-60-41034
JP-A-60-153040, JP-A-60-357
29, JP-A-61-32839, JP-A-61-32
845, JP-A-61-43737, JP-A-61-4
3739, JP-A-61-45346, JP-A-61-
147249, JP-A 61-173246, JP-A 61-267045, JP-A 61-269147,
JP-A-62-80647, JP-A-62-147457
No. 61-196239, 61-196.
240, JP-A-61-83532, JP-A-62-1
68139, JP-A-1-221737.

Examples of the photographically useful reagents used in the precursor for the photographically useful reagents used in the present invention include mercaptotetrazoles, mercaptothiadiazoles, mercaptotriazoles, mercaptoimidazoles, mercaptooxadiazoles and mercaptothiazoles. Antifoggants typified by compounds, benzotriazoles, or indazoles, developing agents typified by pyrazolidones, or hydroquinones, hydrazines, hydrazides, quaternary salts, acetylenes, etc. Nucleating agents, thioethers, silver halide solvents such as hypo or rhodanines, azo dyes,
Examples thereof include a photographically useful reagent having a redox function that releases the above photographically useful reagent as a function of development, a preservative, an antifungal agent, and the like.

In particular, the effect of the present invention becomes remarkable among the photographically useful reagents produced by releasing the blocking group from the precursor of the photographically useful reagent used in the present invention, in that the effect of the present invention becomes remarkable. From this point of view, compounds that are easily adsorbed on silver halide grains are preferable, and examples thereof include the above-mentioned antifoggants.

Specific examples of the photographically useful reagent precursors used in the present invention will be given below, but the scope of the present invention is not limited to these.

[0017]

[Chemical 2]

[0018]

[Chemical 3]

[0019]

[Chemical 4]

The precursor of the photographically useful reagent used in the present invention, including these compounds described above, may be added at any stage during the preparation of the silver halide photographic emulsion, but it may be added after the middle stage of the chemical ripening process. Is preferred,
The period from the end of the same process to immediately before coating is more preferable. These photographically useful reagent precursors are usually added in an amount of 1 × 10 ^-5 mol to 0.01 mol per mol of silver halide.
Molar is preferable, and more preferably 1 × 10 ^{−4 to} 5 × 10.
^-3 mol.

The spectral sensitizing dye used in the present invention may be any one as long as it satisfies the above-mentioned sensitivity ratio and / or absorbance ratio and has a maximum sensitization at 730 nm or more. The compounds represented by I) are useful. General formula (I)

[0022]

[Chemical 5]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents a sulfur atom or a selenium atom. Y ₁ and Y ₄ represent a hydrogen atom, and Y ₁ when Y ₂ is not a hydrogen atom and Y ₄ when Y ₅ is not a hydrogen atom also represent a methyl group, an ethyl group, a hydroxy group or a methoxy group. Y ₂ , Y ₃ , Y ₅ and Y ₆ are hydrogen atoms and optionally substituted alkyl groups having 3 or less carbon atoms (more preferably, for example, methyl group, ethyl group, propyl group, methoxymethyl group, hydroxyethyl group). Group, etc.), halogen atom (eg, chloro atom, bromo atom, etc.), hydroxy group, methoxy group, ethoxy group, monocyclic aryl group (more preferably, for example, phenyl group, tolyl group, anisyl group, 2- Pyridyl group, 4-pyridyl group, 2-thienyl group, 2-furyl group, etc.), acetylamino group and propionylamino group, and Y ₂ is Y ₁ or Y ₃ .
Y _{5 and} Y ₄ or Y ₆ are linked to each other and represent a methylenedioxy group, trimethylene group, tetramethylene group or tetradehydrotetramethylene group. R ₁ and R
_2's may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms. More preferable substituents of the alkyl group and the alkenyl group include, for example, a sulfo group, a carboxy group, a halogen atom, a hydroxy group, an alkoxy group having 6 or less carbon atoms, and an optionally substituted aryl group having 12 or less carbon atoms (eg, , Phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, naphthyl group, 5-methylnaphthyl group,
4-sulfonaphthyl group, etc.), heterocyclic group (eg, furyl group, thienyl group, etc.), C12 or less optionally substituted aryloxy group (eg, chlorophenoxy group, phenoxy group, sulfophenoxy group, Hydroxyphenoxy group, naphthyloxy group, etc., acyl group having 8 or less carbon atoms (eg, benzenesulfonyl group, methanesulfonyl group, acetyl group, propionyl group, etc.), alkoxycarbonyl group having 6 or less carbon atoms (eg, ethoxycarbonyl group) , Butoxycarbonyl group, etc.), cyano group, alkylthio group having 6 or less carbon atoms (eg, methylthio group, ethylthio group, etc.), optionally substituted arylthio group having 8 or less carbon atoms (eg, phenylthio group, tolylthio group, etc.) ), An optionally substituted carbamoyl group having 8 or less carbon atoms (eg, Moyl group, N-ethylcarbamoyl group, etc.), acylamino group having 8 or less carbon atoms (eg, acetylamino group, methanesulfonylamino group, etc.), acylaminocarbonyl group having 8 or less carbon atoms (eg, acetylaminocarbonyl group, methane) Sulfonylaminocarbonyl group, etc.), a ureido group having 7 or less carbon atoms (for example, 3-
Ethyl ureido group, 3,3-dimethyl ureido group, etc.) and the like. It may have one or more substituents.
R ₃ and R ₅ represent a hydrogen atom, and R ₃ is R ₁ and R
₅ represents that R ₂ and R ₂ can be respectively connected to form a 5-membered ring or a 6-membered ring. R ₄ represents a hydrogen atom or an optionally substituted lower alkyl group. R ₆ is a hydrogen atom,
It represents a methyl group, an ethyl group or a propyl group, and R ₇ represents an optionally substituted lower alkyl group or an optionally substituted phenyl group. X represents a counter ion necessary for neutralizing the charge. n represents 0 or 1, and is 0 in the case of an intramolecular salt.

Specific examples of the above-mentioned nitrogen-containing heteronuclear nucleus in which Z ₁ and Z ₂ are represented as one of the constituent atom groups include, for example, benzothiazole, 4-methylbenzothiazole, 4-chlorobenzothiazole, 4-methoxybenzothiazole, 4-methyl-5-chloro-benzothiazole, 4-methoxy-5-chlorobenzothiazole,
4-methylbenzothiazole, 5-methylbenzothiazole, 5-ethylbenzothiazole, 5-propylbenzothiazole, 5,6-dimethylbenzothiazole, 5
-Methoxybenzothiazole, 5-ethoxybenzothiazole, 5,6-dimethoxybenzothiazole, 5-methoxy-6-methylbenzothiazole, 5-phenylbenzothiazole, 5-p-tolylbenzothiazole, 5
-Acetylaminobenzothiazole, 5-propionylaminobenzothiazole, 5-hydroxybenzothiazole, 5-hydroxy-6-methylbenzothiazole,
5,6-dioxymethylenebenzothiazole, 4,5-
Dioxymethylenebenzothiazole, 5,6-trimethylenebenzothiazole, naphtho [1,2-d] thiazole, 5-methylnaphtho [1,2-d] thiazole, 8-
Methoxynaphtho [1,2-d] thiazole, 8,9-dihydronaphthothiazole, benzoselenazole, 4-methoxybenzoselenazole, 4,5-dimethoxybenzoselenazole, 5-methylbenzoselenazole, 5-ethylbenzo Selenazole, 5-methoxybenzoselenazole, 5-ethoxybenzoselenazole, 5,6-dimethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-hydroxy-6-methylbenzoselenazole, naphtho [1,2- d] selenazole and the like.

Specific examples of the groups represented by R ₁ and R ₂ are:
For example, methyl group, ethyl group, propyl group, allyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group, phenethyl group, triethyl group, phenoxyethyl group, phenoxypropyl group, naphthoxyethyl group, sulfophenethyl group, 2, 2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2- (2-hydroxyethoxy) ethyl group, carboxymethyl group, carboxyethyl group, ethoxy Carbonylmethyl group, sulfoethyl group, 2-chloro-3-sulfopropyl group, 3-
Sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
(2,3-dihydroxypropyloxy) ethyl group, 2
Examples thereof include-[2- (3-sulfopropyloxy) ethoxy] ethyl group, acetylaminoethyl group, methylsulfonylaminoethyl group, methylsulfonylaminocarbonylethyl group, acetylanilinocarbonylethyl group and the like. Preferred specific examples of the optionally substituted lower alkyl group represented by R ₄ include a methyl group, an ethyl group, a propyl group and a benzyl group, and the optionally substituted lower alkyl group or the substituted group represented by R ₇ Preferred specific examples of the phenyl group which may be present include a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a phenyl group, a p-methoxyphenyl group, a p-tolyl group and the like. Specific examples of the counter ion represented by X ₁ include:
Examples of the cation include alkali metal ions such as potassium and sodium, ammonium ions such as triethylammonium and N, N-dimethylbenzylammonium, immonium ions such as pyridinium, and chloride ions and bromine ions when the anion is used. Examples thereof include halide ions such as iodine ions, sulfonate ions such as p-toluenesulfonate and benzenesulfonate, and carboxylate ions such as acetate.

In the sensitizing dye represented by the general formula (I), a more preferable sensitizing dye is one of Z ₁ and Z ₂ among the sensitizing dyes represented by the general formula (I). When at least one of them represents a sulfur atom, Y ₁ and Y
₄ represents a hydrogen atom, and Y ₂ and Y ₅ represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxymethyl group, a hydroxyethyl group, a hydroxy group, a methoxy group, an ethoxy group, a phenyl group and an acetylamino group. In addition, Y ₂ is Y ₃ and Y ₅ is Y ₆ , and each represents a methylenedioxy group, a tetramethylene group or a tetrahydrotetramethylene group, and Y ₃ and Y ₆ represent a hydrogen atom or a methoxy group, and , R ₆ represents a hydrogen atom.

Next, specific examples of the sensitizing dye represented by the general formula (I) will be listed in order to more specifically explain the content of the present invention, but the present invention is limited to these compounds. is not.

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

The sensitizing dye represented by the general formula (I) used in the present invention is a known compound, and is disclosed in, for example, JP-A-SHO-5.
No. 2-104,917, Japanese Patent Publication No. 48-25,652,
Japanese Patent Publication No. 57-222, 268, etc., and F. M. H
Amer, The Chemistry of Het
Erocyclic Compounds, Vol. 1
8, The Cyanine Dyes and Re
later compounds, A.M. Weissbe
rger ed. , Interscience, New
York, 1964. , D. M. Sturmer, T
he Chemistry of Heterocyc
lic Compounds, Vol. 30, A.I. We
issberger and E.I. C. Taylor
ed. , Jhon Willy, New York,
p. 441. , Japanese Patent Application No. 2-270,164, etc.

To incorporate the cyanine dye represented by formula (I) used in the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol , Ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. The method described in JP-B-46-24,185, etc.,
A method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion.
No. 23,389, JP-B-44-27,555, JP-B-57-22,091, etc., the dye is dissolved in an acid and the solution is added to the emulsion, or the acid or A method in which a base is allowed to coexist to form an aqueous solution and added to the emulsion,
US Pat. No. 3,822,135, US Pat.
No. 025, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion, JP-A-53-102,733, JP-A-58-105, No. 141, a method in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. A dye is prepared by using a red-shifting compound as described in JP-A-51-74624. It is also possible to use a method in which is dissolved and the solution is added to the emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any stage during the preparation of emulsions which have been found to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749, and the like, as disclosed in the specification, silver halide grain forming step and / or timing before desalting, during desalting step and / or desalting step. From the time after salting to before the start of chemical aging, JP-A-58-1
As disclosed in the specification of No. 13,920, etc., it is added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated until after the chemical ripening and before the coating. May be. US Pat. No. 4,225,6
No. 66, JP-A-58-7,629 and the like, the same compound alone or in combination with a compound having a different structure, for example, in the same step or in the particle forming step. And the chemical aging step or after the chemical aging is completed, or may be added separately in different steps such as before the chemical aging or during and after the chemical aging. The combination type may be changed and added. In addition, a predetermined amount may be added in a short time, or may be continuously added for a long time, for example, after the nucleation in the grain forming process to the completion of grain formation or most of the chemical ripening process. The more preferable addition time is any time from the nucleus formation in the silver halide grain forming step to the first half of the chemical ripening step.

The silver halide used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide and silver iodobromide. The silver halide emulsion used in the present invention may contain these silver halide grains singly or as a mixture of plural grains. The silver halide grains may have different phases in the inside and the surface, may have a multi-phase structure having a junction structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. It may consist of phases. Moreover, they may be mixed. The silver halide grains used in the present invention may be monodisperse or polydisperse, and the shape thereof may be one having a regular crystal such as a cube, octahedron or tetradecahedron, or an irregular ( It may have an irregular crystal form,
Further, it may have a composite form of these crystal forms. Further, tabular grains may be used, and tabular grains having a ratio of equivalent circle diameter / grain thickness of silver halide grains of 5 or more, particularly 8 or more may be an emulsion occupying 50% or more of the total projected area of grains. Further, it may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is described by Grafkid, "The Chemistry and Physics of Photography" (P. Glafkides, Chemie et P.
hysique Photographique, Paul Montel, 1967.), Duffin, "Photoemulsion Chemistry" (GFDaffin, Photographic Emu
lsion Chemistry, Focal Press, 1966.), Zelikman et al., "Manufacturing and Coating of Photographic Emulsions" (VL Zelikman et al., Mak
ing and Coating Photographic Emulsion, Focal Pres
s, 1964.), FHClaes et al., The Journal of Photo.
graphic Science, (21) 39-50, 1973. and FHClaes et
al., The Journal of Photographic Science, (21) 85〜
92, 1973., Japanese Patent Publication No. 55-42,737, US Pat. No. 4,400,463, US Pat. No. 4,80.
1,523, JP-A-62-218,959, 63.
-213,836, 63-218,938, Japanese Patent Application No. 62-291,487 and the like. That is, the acidic method, the neutral method,
The ammonia method or the like may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, or the like. A method of forming grains in the presence of excess silver (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method including a process of converting into silver halide which has already been formed by the time the silver halide grain forming process is completed, and after the silver halide grain forming process is completed. Emulsions which have undergone similar halogen conversion can also be used.

A silver halide solvent may be used during the production of the silver halide grains of the present invention. As a silver halide solvent often used, for example, a thioether compound (for example, US Pat. Nos. 3,271,157 and 3,57,57) is used.
4,628, 3,704,130, 4,27
6,347), thione compounds and thiourea compounds (for example, JP-A Nos. 53-144,319 and 53-8).
No. 2,408, No. 55-77,737, etc.), amine compounds (for example, JP-A No. 54-100,717, etc.) and the like, and these can be used. Ammonia can also be used within a range that does not have any adverse effect. During the production of the silver halide grains of the present invention, in order to accelerate the grain growth, the addition rate, the addition amount and the addition concentration of the silver salt solution (for example, silver nitrate aqueous solution) and the halide solution (for example, saline aqueous solution) to be added are set to the time. The method of increasing the temperature is preferably used. Regarding these methods, for example, British Patent 1,335,925 and US Pat.
72,900, 3,650,757, 4,24
2,445, JP-A-55-142,329, and 55.
-158,124, 55-113,927, 5
It can be referred to the description of 8-113,928, 58-111,934, 58-111,936, etc.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, potassium salt, rhenium salt, ruthenium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or You may make the complex salt etc. coexist. Particularly, rhenium salt, iridium salt, rhodium salt, or iron salt is more preferable. As the addition amount of these, any amount can be added as necessary. For example, iridium salts (for example, Na ₃ IrCl ₆ , Na ₂ Ir
_{Cl 6, Na 3 Ir (CN} ) 6 , etc.), per mol of silver 1 × 10 ^-8 or more, an amount in the range of 1 × 10 ^-5 or less, rhodium salts _{(e.g., RhCl 3, K 3 Rh (} CN ) ₆ etc.) is 1 × 10 per mol of silver.
^-8 above, an amount in the range of 1 × 10 ^-8 or less.

The silver halide emulsion of the present invention may remain unchemically sensitized, but can be chemically sensitized if necessary. As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. Nos. 2,448,060 and 3,320,069) or a sensitization method using a metal such as iridium, platinum, rhodium or palladium is used. (For example, US Pat. Nos. 2,448,060 and 2,566,245,
No. 2,566,263), or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,264).
), A selenium sensitization method using a selenium compound, or a reduction sensitization method using a tin salt, thiourea dioxide, polyamide or the like (see, for example, US Pat. Nos. 2,487,850 and 2,51).
No. 8,698, No. 2,521,925), or a combination of two or more thereof. The silver halide emulsion of the present invention is more preferably gold-sensitized or sulfur-sensitized, or a combination thereof. The preferred amount of gold sensitizer and sulfur sensitizer added is 1 × 10 ⁻⁷ to 1 mol of silver, respectively.
1 × 10 ⁻² mol, more preferably 5 × 10 ⁻⁶ to 1
It is × 10 ^-3 . When gold sensitization and sulfur sensitization are used together, the preferable ratio of the gold sensitizer and the sulfur sensitizer is 1: 3 to a molar ratio.
It is 3: 1 and more preferably 1: 2 to 2: 1.
The temperature for carrying out the chemical sensitization of the present invention is from 30 ° C to 90 ° C.
It can be selected from any temperature between ° C. The pH during the chemical sensitization is 4.5 to 9.0, preferably 5.0.
To 7.0. The time of chemical sensitization cannot be decided unconditionally because it varies depending on temperature, type and amount of chemical sensitizer used, pH, etc., but it can be arbitrarily selected from several minutes to several hours, usually from 10 minutes. It takes place in 200 minutes.

The sensitizing dye used in the present invention, including the sensitizing dye represented by the general formula (I), enhances its adsorption to silver halide and the formation of J-aggregate to obtain higher spectral sensitivity. Water-soluble iodide salts such as potassium iodide, water-soluble bromide salts such as potassium bromide, and water-soluble thiocyanates such as potassium thiocyanate are often used in combination, but in the present invention. The water-soluble bromide salt and water-soluble thiocyanate are particularly effective when they are silver chloride or silver chlorobromide having a high silver chloride content. A high silver chloride emulsion having a silver chloride content of 50 mol% or more is preferred in order to achieve ultra-rapid processing in which the development time is 30 seconds or less. For this purpose, as is well known, the iodine ion has a strong development inhibitory property, and the iodine ion including the above water-soluble iodide salt is 0.05 mol% per mol of silver.
It is preferable to suppress it to the following. In order to produce a silver halide light-sensitive material suitable for ultra-rapid processing, a silver chloride content of 80
A high-silver chloride emulsion having a mol% or more is more preferable. In such an emulsion, as described above, the combined use of a water-soluble bromide salt and / or a water-soluble thiocyanate enhances the formation of J-aggregate and has a higher spectral sensitivity. However, the addition amount thereof is preferably in the range of 0.03 to 3 mol%, particularly preferably 0.08 to 1 mol% per mol of silver.

In the case of high silver chloride grains having a silver chloride content of 80 mol% or more, high sensitivity is obtained when infrared spectral sensitization is performed, and stability thereof, particularly excellent latent image stability is obtained. High silver chloride grains having a localized phase in the grains, which are disclosed in JP-A-2-248,945 and the like, which have the following characteristics are more preferable. As disclosed in the above patent, the silver bromide content of this localized phase is preferably more than 15 mol%, particularly preferably 20 to 60 mol%, more preferably 30 to 50 mol%. Most preferably, the balance is silver chloride in the range of. Further, the localized phase may be inside the silver halide grain, may be on the surface or sub-surface, and may be divided into the surface or sub-surface. The localized phase may have a layered structure surrounding the silver halide grains or may have a discontinuously independent structure inside or on the surface. A preferred specific example of the arrangement of the localized phase having a higher silver bromide content than the surroundings, the localized phase having a silver bromide content of at least 15 mol% locally epitaxially grown on the surface of the silver halide grain. It is a thing. The silver bromide content of the localized phase can be determined by an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) or XPS method (for example, surface analysis, IMA). , "Application of Auger electron / photoelectron spectroscopy" Kodansha, Ltd.) and the like. The localized phase is preferably composed of 0.1 to 20% of silver of the total amount of silver constituting the silver halide grains, and more preferably 0.5 to 7% of silver. preferable.

The interface between the localized phase having a high silver bromide content and the other phase may have a clear phase boundary, or may have a short transition region in which the halogen composition gradually changes. You can do it. In order to form such a localized phase having a high silver bromide content, various methods can be used. For example, a soluble silver salt and a soluble halogen salt can be reacted by a one-sided mixing method or a simultaneous mixing method to form a localized phase. Further, the localized phase can be formed by using a so-called conversion method including a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can be formed by recrystallizing the surface of silver chloride grains by adding fine silver bromide grains.

Further, in order to further enhance the effects of the present invention, the silver halide emulsion according to the present invention may be represented by the following general formula (II) or general formula (III). It is more preferable to include a sensitizing dye in combination with the tetrazaindene compound represented. General formula (II)

[0045]

[Chemical 10]

General formula (III)

[0047]

[Chemical 11]

In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different and each is a hydrogen atom or a total carbon number of 1 to 1.
An unsubstituted or substituted alkyl group which may have 20 rings or branches, a monocyclic or bicyclic unsubstituted or substituted aryl group, an unsubstituted or substituted amino group,
Hydroxy group, alkoxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 6 carbon atoms, carbamoyl group which may be substituted with aliphatic group or aromatic group, halogen atom, cyano group, carboxy group, total It represents an alkoxycarbonyl group having 2 to 20 carbon atoms, or a heterocyclic residue containing a 5- or 6-membered ring having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. R ²¹ and R ²² or R ²² and R ²³ may combine to form a 5- or 6-membered ring.
However, at least one of R ²¹ and R ²³ represents a hydroxy group.

Examples of the unsubstituted alkyl group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-propyl group, n-butyl group, t-butyl group,
Hexyl group, cyclohexyl group, cyclopentylmethyl group, octyl group, dodecyl group, tridecyl group, heptadecyl group and the like can be mentioned. Examples of the substituent in the substituted alkyl group include, for example, monocyclic or bicyclic aryl groups, hetero residues, halogen atoms, carboxy groups, alkoxycarbonyl groups having 2 to 6 carbon atoms, and those having 19 or less carbon atoms. Examples thereof include alkoxy group and hydroxy group, and specific examples of the substituted alkyl group include, for example, benzyl group, phenethyl group, chloromethyl group, 2-chloroethyl group, trifluoromethyl group, carboxymethyl group, and 2-carboxyethyl group. , 2- (methoxycarbonyl) ethyl group, ethoxycarbonylmethyl group, 2-methoxyethyl group, hydroxymethyl group, 2-hydroxyethyl group and the like. Examples of the above-mentioned unsubstituted aryl group include, for example, a phenyl group and a naphthyl group, and examples of the substituent when the aryl group is substituted include, for example, an alkyl group having 4 or less carbon atoms, a halogen atom, Examples thereof include a carboxy group, a cyano group, an alkoxycarbonyl group having 6 or less carbon atoms, a hydroxy group, an alkoxy group having 6 or less carbon atoms, and specific examples of the substituted aryl group include, for example, p-tolyl group,
m-tolyl group, p-chlorophenyl group, p-bromophenyl group, o-chlorophenyl group, m-cyanophenyl group, p-carboxyphenyl group, o-carboxyphenyl group, 0- (methoxycarbonyl) phenyl group, p- Examples thereof include a hydroxyphenyl group, p-methoxyphenyl group and m-ethoxyphenyl group. Examples of the substituent of the above-mentioned substituted amino group include, for example, an alkyl group (eg, methyl group, ethyl group, butyl group), an acyl group (eg, acetyl group, propionyl group, benzoyl group, methylsulfonyl group) and the like. Specific examples of the substituted amino group include, for example, a dimethylamino group, a diethylamino group, a butylamino group and an acetylamino group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, a heptadecyloxy group and the like. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a hexylthio group and the like. The above-mentioned carbamoyl group can have one or two alkyl groups having 20 or less carbon atoms and two or less aryl groups as a substituent. Specific examples of the substituted carbamoyl group include a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group and a phenylcarbamoyl group. Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Specific examples of the halogen atom are fluorine atom, chlorine atom and bromine atom. The heterocyclic residue may have a monocyclic ring or a condensed ring of 2 to 3 rings, and specific examples thereof include a furyl group, a pyridyl group and 2- (3
-Methyl) benzothiazolyl group, 1-benzotriazolyl group and the like. In the above-mentioned substituted alkyl group,
When the substituent of the substituted alkyl group represented by R ²⁴ is a heterocyclic residue, the substituent represented by the following formula (IV) is preferable. General formula (IV)

[0050]

[Chemical 12]

In the above formula, R ²¹ , R ²² and R ²³ have the same meanings as described above, and n represents 2, 3 or 4. In the present invention, the compound represented by the general formula (II) or the general formula (III) is 1 × 10 ⁻⁵ per mol of silver halide.
0.2 moles, in particular, 3 × 10 ^-4 to 0.02 may be contained in a molar range, the addition amount of the compound, the particle size of the silver halide emulsion, the halogen composition, the degree and method of chemical sensitization It is desirable to select the optimum amount depending on the relationship between the emulsion layer according to the present invention and other layers, the kind of the fog-preventing compound, and the like. The test method for the selection is well known to those skilled in the art and is easy for those skilled in the art. In the present invention, the compound represented by the general formula (II) or the general formula (III) is contained in the silver halide emulsion according to the present invention by the formula (I). The compound may be directly dispersed in the emulsion in the same manner as the addition method of the cyanine dye described above, or a solution of an organic solvent miscible with water, or an aqueous solution when water-soluble, or What is dispersed in the hydrophilic colloid solution may be added. It may be convenient to dissolve in an alkaline aqueous solution. In the present invention, the general formula (II) or the general formula (III)
When the compound represented by any of the above is added to the silver halide emulsion, the addition may be performed at any time from the step of forming silver halide grains to the coating of the silver halide emulsion. Select an appropriate amount depending on the type of silver halide and the grain size within the range of 3 × 10 ⁻³ mol or less per 1 mol of silver (the absorption intensity by the sensitizing dye does not decrease or is rather sharp and the absorption intensity is high). It is more preferable to add the cyanine dye represented by the general formula (I) before the addition, and in the case of a high silver chloride emulsion, it is more preferable to add the amount before the start of chemical ripening. . With such an addition method, the fog can be more effectively suppressed and the sensitivity can be further enhanced.

Specific examples of the compounds represented by the general formula (II) or the general formula (III) are shown below, but the present invention is not limited to these specific compounds.

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

The silver halide emulsion of the present invention may contain a methine dye and / or a supersensitizer other than the cyanine dye according to the present invention for the purpose of expanding the light-sensitive wavelength range and supersensitizing. Well, when the silver halide grains other than the silver halide grains according to the present invention are contained in the same layer or different layers, the silver halide grains include not only the cyanine dye according to the present invention but also other methine dyes and strong dyes. It may be spectrally sensitized with a color sensitizer.

Examples of dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, cytylyl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, selenazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tellurazole nucleus, pyridine nucleus, tetrazole nucleus, etc .; Condensed nuclei; and nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, that is, indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzimidazole nuclei, naphthimidazole nuclei, benzo A thiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterrazole nucleus and the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the complex merocyanine dye, as the nucleus having a ketomethylene structure, any nucleus generally used for merocyanine dyes can be applied. Particularly useful nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidine-2,4-
Applying 5-membered and 6-membered heterocyclic nuclei such as dione nucleus, thiozolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, 2-thioselenazolidine-2,4-dione nucleus You can

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is
Especially, it is often used for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,2.
No. 29, No. 3,397,060, No. 3,522,05
No. 2, No. 3,527, 641, No. 3, 617, 293
No. 3,628,964, 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,703,377, No. 3,769,301
Nos. 3,614,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1,507,803, Japanese Patent Publication No. 43-4.9
36, 53-12,375, JP-A-52-11.
0,618, 52-109,925 and the like.

As a typical example of the supersensitizer, Japanese Patent Laid-Open No. 59-59
-142,541 and the like, bispyridinium salt compounds, stilbene derivatives as described in JP-B-59-18,691 and the like, water-soluble bromides disclosed in JP-B-49-46,932 and US Pat. , 743, 510, a condensate of an aromatic compound and formaldehyde, a cadmium salt, an azaindene compound, and the like.

The timing of adding these methine dyes to the silver halide emulsion may be any stage of emulsion preparation known to be useful so far, and the addition method and the addition amount have been useful so far. Any method and amount known to be. Specifically, the addition timing of the cyanine dye represented by the general formula (I), the addition method,
In addition, the timing, the addition method, and the addition amount described as the addition amount can be mentioned.

The silver halide photographic emulsion used in the present technology may be variously incorporated for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be included. That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzotriazoles, nitrobenzotriazoles,
Mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4 -Hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Also, many compounds can be added.

The color coupler used in the present invention is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule, or a polymerized type. The coupler has 4 equivalents or 2 with respect to silver ion.
Either equivalence may be used. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. Further, the product of the coupling reaction may be colorless and may contain a colorless DIR coupling compound which releases a development inhibitor.

Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers. (For example, benzoylacetanilides, pivaloylacetanilides), and the like, and cyan couplers include naphthol couplers and phenol couplers. U.S. Pat. Nos. 3,772,002 and 27,721 as cyan couplers.
No. 62, No. 3758308, No. 4126396,
No. 4334011, No. 4327173, No. 3446
No. 622, No. 4333999, No. 4451559,
No. 4,427,767, etc., a phenolic coupler having an ethyl group at the meta position of the phenol nucleus, a 2,5-diacylamino-substituted phenolic coupler, a phenolic coupler having a phenolureido group at the 2-position and an acylamino group at the 5-position. A coupler and a coupler in which a sulfonamide, an amide or the like is substituted at the 5-position of naphthol are preferable because the image fastness is excellent.

Examples of such more preferable color couplers include JP-A-2-248,945, pages 22 to 30.
The same thing as what was indicated by the page is mentioned.

The above-mentioned couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for a light-sensitive material, and the same compound can be added in two or more different layers, as a matter of course. Absent.

The color coupler is usually preferably used in the silver halide emulsion layer constituting the light-sensitive layer, preferably 0.1 to 1.0 mol, and more preferably 0.1 to 0 mol, per mol of silver halide. It is contained in an amount of 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. After being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by the so-called Fisher dispersion method. The low boiling point organic solvent may be removed from the coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion.

The dispersion medium of such a coupler has a dielectric constant (25 ° C.) of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.
It is preferable to use the high boiling point organic solvent of 7 and / or the water-insoluble polymer compound.

As the high-boiling point organic solvent, those disclosed in JP-A-2-248,945, page 30 can be mentioned as preferable ones. For details thereof, see JP-A-62-215. No. 272, pp. 137-1
It is described on page 44.

These couplers are also loadable latex polymers in the presence or absence of the above high boiling organic solvents (eg US Pat. No. 4,203,716).
It can be emulsified and dispersed in a hydrophilic colloid aqueous solution by being impregnated with or dissolved in a water-insoluble and organic solvent-soluble polymer.

International publication WO88 / 00723 is preferred.
The homopolymers or copolymers described on pages 12 to 30 of the specification are used, and the use of an acrylamide polymer is particularly preferable in terms of color image stabilization and the like.

The light-sensitive material produced by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color fog inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, cyan, magenta and /
Alternatively, as an organic anti-fading agent for yellow images, hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives Representative examples thereof include methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Also (bissalicylaldoximato)
A metal complex represented by a nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the specifications of the following patents. Hydroquinones include U.S. Pat. Nos. 2,360,290, 2,418,613, 2,700,453, and 2,701,197.
No. 2,728,659, No. 2,732,300
No. 2,735,765, 3,982,94
No. 4, No. 4,430,425, and British Patent No. 1,36.
No. 3,921, U.S. Pat. Nos. 2,710,801, 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are described in U.S. Pat. No. 3,573,05
No. 0, No. 3,574,627, No. 3,698, 9
09, No. 3,764,337, JP-A-52-15.
2225, spiroindanes are described in US Pat.
360,589, p-alkoxyphenols are described in U.S. Pat. No. 2,735,765 and British Patent 2,06.
6,975, JP-A-59-10539, JP-B-57.
-19765 and the like, hindered phenols are disclosed in U.S. Pat. No. 3,700,455 and Japanese Patent Publication No. 52-72224.
No. 4,228,235, Japanese Patent Publication No. 52-6.
No. 223, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in US Pat. Nos. 3,457,079, 4,332,886, and Japanese Patent Publication No. 56-21114, respectively. Classes include U.S. Pat. Nos. 3,336,135 and 4,268,
593, British Patents 1,326,889, 1,
354, 313, 1.410, 846, JP-B-51-1420, JP-A-58-114036, 59-53846, 59-78344, and the like.
Metal complexes are disclosed in U.S. Pat. Nos. 4,050,938,
241,155, British Patent No. 2,027,731
(A) and the like, respectively. These compounds can achieve the object by usually coemulsifying 5 to 100% by weight of the corresponding color coupler with the coupler and adding them to the photosensitive layer. In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to the cyan coloring layer.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794) and a 4-thiazoadone compound (for example, US Pat. No. 3,314,794) are used. No. 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
705,805 and 3,707,395), butadiene compounds (US Pat. No. 4,045,22).
No. 9) or a benzooxide compound (for example, those described in US Pat. No. 3,700,455) can be used. UV absorbing couplers (eg α-naphthol cyan dye forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These UV absorbers may be mordanted in a specific layer.

Among them, the benzotriazole compound substituted with the above aryl group is preferable. Further, it is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and // which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing.

The preferred compound (F) is p-
Second-order reaction rate constant k with anisidine ₂(80 ℃ trio
In octyl phosphate) 1.0 l / mol.sec to 1 ×
Ten^-FiveIt is a compound that reacts in the range of 1 / mol.sec. Na
The second-order reaction rate constant is described in JP-A-63-158545.
It can be measured by the method described.

If k ₂ is larger than this range, the compound itself may become unstable and may react with gelatin or water to decompose. On the other hand, when k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compounds (F) can be represented by the following general formula (FI) or (FII). General formula (FI)

[0083]

[Chemical 17]

Formula (FII)

[0085]

[Chemical 18]

In the formula, R ₁₀₁ and R ₁₀₂ each represent an aliphatic group, an aromatic group or a heterocyclic group. n ₁₀₁ represents 1 or 0. A reacts with an aromatic amine-based developer,
It represents a group that forms a chemical bond, and Y ₁₀₁ represents a group that is released by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y ₁₀₂ represents an aromatic amine developing agent added to the compound of the general formula (FII). Represents a promoting group. Here, R ₁₀₁ and Y ₁₀₁ , Y ₁₀₂ and R ₁₀₂
Alternatively, B and B may be bonded to each other to form a ring structure.

Among the methods of chemically bonding with the residual aromatic amine type developing agent, representative ones are substitution reaction and addition reaction. Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545 and 62-62.
Those described in the specifications such as -283338, Japanese Patent Application No. 62-158342, European Patent Publication Nos. 277589 and 293321 are preferable.

On the other hand, the more preferable compound (G) which is chemically inactive and colorless compound by chemically bonding with the oxidation product of the aromatic amine type developing agent remaining after the color development processing is as follows. It can be represented by formula (GI). General formula (G1)

[0089]

[Chemical 19]

In the formula, R ₁₀₃ represents an aliphatic group, an aromatic group or a heterocyclic group. Y ₁₀₃ represents a nucleophilic group or a group which decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (G1), Y ₁₀₃ is Pearson's nucleophilic “CH ₂ I value (RG Pearson. Et al., J. Am. Chem. Soc., 9
A group in which 0,319 (1968)) is 5 or more, or a group derived therefrom is preferable.

Specific examples of the compound represented by the general formula (GI) are described in European Patent Publication No. 255722, JP-A-6-62.
2-143048, 62-229145, JP-A-1-230039, JP-A-1-57259, and JP-A-64.
-2042 and European Patent Publication 277589 and 298.
Those described in No. 321 and the like are preferable.

The details of the combination of the compound (G) and the compound (F) are described in European Patent Publication 277589. The light-sensitive material produced by the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer.
For example, a benzotriazole compound substituted with an aryl group (also described in, for example, US Pat. No. 3,533,794), a 4-thiazolidone compound (for example, US Pat.
314,794 and 3,352,681), benzophenone compounds (for example, JP-A-46-27).
84 also), cinnamic acid ester compounds (for example, US Pat. Nos. 3,705,805 and 3,707,37).
5), a butadiene compound (for example, those described in US Pat. No. 4,045,229), or a benzooxide compound (for example, US Pat. No. 3,70).
Those described in No. 0,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol type cyan dye forming coupler), an ultraviolet absorbing polymer or the like may be used. These UV absorbers may be mordanted in a specific layer.

Colloidal silver and dyes are used in the full-color recording material of the present invention for preventing irradiation and halation, especially for separating the spectral sensitivity distribution of each photosensitive layer and ensuring safety against safelight in the visible wavelength range. To be Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

Particularly, red dyes or infrared dyes are disclosed in, for example, JP-A Nos. 62-3250, 62-181381, and 62-62.
No. 123345, No. 63-197947, etc., decolorizable dyes, back employment and Japanese Patent Laid-Open No. 62-
No. 39682, No. 62-123192, No. 62-15
The dyes described in No. 877 and No. 62-174741 or the dyes can be used by introducing a water-soluble group capable of flowing out during the treatment. The infrared dye of the present invention may be a colorless dye that does not substantially absorb light in the visible wavelength range.

The infrared dye of the present invention, when mixed with a silver halide emulsion spectrally sensitized in the red end to infrared wavelength region,
There are problems such as desensitization, generation of fog, and in some cases, the dye itself is adsorbed on the silver halide grains to cause weak broad spectral sensitization. Preferably only in the colloidal layer other than the photosensitive layer,
It is preferable to contain substantially. For this purpose, the dye may be contained in a predetermined colored layer in a diffusion resistant state. The first is to make the dye resistant to diffusion by incorporating ballast groups. However, residual color and processing stain are likely to occur. Second, the anionic dye of the present invention is mordanted together with a polymer or polymer latex that provides a cation site. Thirdly, fine particles of a dye that is insoluble in water having a pH of 7 or less and that is decolorized and eluted during the process are dispersed and used. For that purpose, it is dissolved in a low boiling point organic solvent or solubilized in a surfactant, and this is dispersed in a hydrophilic protective colloid aqueous solution such as gelatin for use. Preferably, the solid of the dye is kneaded with an aqueous surfactant solution and mechanically made into fine particles by a mill, which is dispersed in an aqueous hydrophilic colloid solution such as gelatin.

As the binder or protective colloid that can be used in the light-sensitive layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in "The Macromolecular Chemistry of Gelatin (Academic Press, 1964)" by Arthur Weiss.

The full-color light-sensitive material using the present invention comprises a light-sensitive layer (Y) containing a yellow coupler on a support.
L), a photosensitive layer (ML) containing a magenta coupler,
Cyan coupler-containing photosensitive layer (CL), protective layer (P
L), an intermediate layer (IL), and if necessary, a decolorizable color layer, especially an antihalation layer (AH), is provided during the development processing. YL, ML, and CL have spectral sensitivities adapted to at least three types of light beams having different dominant wavelengths. YL,
The main sensitivity wavelengths of ML and CL are respectively 30 nm or more, preferably 50 nm to 100 nm, and at the main sensitivity wavelength of one photosensitive layer, at least 0.8 Log. There is a sensitivity difference of E (light amount), preferably 1.0 or more, more preferably 1.2 or more. At least one of the photosensitive layers is sensitive to wavelengths longer than 650 nm, and more preferably at least two layers are sensitive to wavelengths longer than 730 nm.

For example, as shown in the following table, an arbitrary photosensitive layer can be formed. In the table, R represents red sensitized, and IR-1 and IR-2 spectrally sensitized in different infrared wavelength regions. Sample 1 2 3 4 Protection layer PL PL PL PL YL = R YL = IR-2 YL = R ML = R Photosensitive layer ML = IR-1 ML = IR-1 CL = IR-1 YL = IR-1 unit CR = IR-2 CL = R MR = IR-2 CL = IR-2 (AH) (AH) (AH) (AH) Support Sample 5 6 7 8 Protective layer PL PL PL PL PL CL = R CL = R CL = IR -2 ML = IR-2 photosensitive layer YL = IR-1 ML = IR-1 ML = IR-1 CL = IR-1 unit ML = IR-2 YL = IR-2 YL = R YL = R (AH) ( AH) (AH) (AH) support sample 9 protective layer PL ML = R photosensitive layer CL = IR-1 unit YL = IR-2 (AH) support

Not only the silver halide emulsion having the maximum wavelength of spectral sensitivity in the wavelength longer than 730 nm used in the present invention,
With respect to the silver halide emulsion not containing the present invention, which is further contained depending on the purpose, a dye may be used for the purpose of further improving the image sharpness and safelight stability and preventing color mixing. The dye may be a layer containing the emulsion or a layer not containing the emulsion, but it is preferably fixed in a specific layer. For that purpose, the dye is contained in the colloid layer in a diffusion resistant state and used so that it can be decolorized during the development process. The first is to use a fine particle dispersion of a dye that is substantially insoluble in water having a pH of 7 and becomes soluble in water having a pH of 7 or more. Second, the use of acid dyes with polymers or polymer latices that provide cation sites. The dyes represented by the general formulas (VI) and (VII) described in JP-A-63-197,947 are useful for the first and second methods. In particular, a dye having a carboxy group is useful in the first method.

There are no particular restrictions on other additives in the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 17
Volume 6 items 17643 (RD17643), 187
Volume item 18716 (RD18716) and 307
The description of the winding item 307105 (RD307105) can be referred to.

RD17643, RD18716 and RD
The places where various additives are described in 307105 are listed below.

Additive type RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Same as above 3. Spectral sensitizers, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggants, pages 24 to 25, page 649, right column, pages 868 to 870, and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column to page 873, Luter dye, purple, page 650, left column, external line absorber 7. Anti-staining agent Page 25 Right column Page 650 Left-Right column Page 872 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Hinder, p. 26, ibid., Pages 873 to 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, surface 26 to 27 pages 650 right column 875 to 876 activator 13. Static prevention page 27 Same as above pages 876 to 877 Agent 14. Matt agent 878 to 879

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate film, which is generally used in a photographic light-sensitive material, or a reflective support can be used. Their thickness is 10
-350 micrometers is preferable and 30-250 micrometers is more preferable.

The "reflective support" used in the present invention is one which enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear, and such a reflective support includes
A support coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein to increase the reflectance in the visible light wavelength range, or a light-reflecting substance dispersedly contained. Those using a hydrophobic resin as a support are included. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate,
There are a polyamide film, a polycarbonate film, a polystyrene film, a vinyl chloride resin and the like, and these supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use a pigment particle whose surface is treated with a dihydric or tetrahydric alcohol.

The occupying area ratio (%) of the white pigment fine particles per defined unit area is most typically observed by dividing the observed area into contiguous 6 μm × 6 μm unit areas. Occupied area ratio of projected particles (%)
(R ₁ ) can be measured and obtained. The coefficient of variation of the occupied area ratio (%) is R ₁ with respect to the average value (Rav) of R _1.
It can be obtained by the ratio s / Rav of the standard deviation s of. The number (n) of the target unit areas is preferably 6 or more. Therefore, the variation coefficient s / Rav can be calculated by the following equation.

[0108]

[Equation 1]

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is 0.15 or less, particularly 0.12.
The following are preferred. A metal thin film such as aluminum or a light alloy is used as the light-reflecting material, for example, JP-A-63-11815.
No. 4, No. 63-24247, No. 63-24251 to No. 63-24251, No. 63-24255, No. 63-24255, etc., and a metal having a specular reflection or a second-class diffuse reflection surface can also be used.

The photographic light-sensitive material of the present invention is, for example, a black-and-white and color negative film for photography (general use, movie), a color reversal film (slide, movie), black and white and color photographic paper, color positive film (movie). , Color reversal printing paper, black and white and color photosensitive materials for heat development, black and white and color photographic photosensitive materials for plate making (lith film, scanner film, etc.), black and white medical and industrial photosensitive materials, black and white and color diffusion transfer photosensitive materials (DTR) and the like.

Next, the luminous flux output mechanism used in the present invention will be described. A semiconductor laser is preferable as the laser that can be used in the present invention, and specific examples thereof include In _1-x Ga _x P (up to 700 nm) and GaAs _1-x P.
_x (610-900 nm), Ga _1-x Al _x As (690
~ 900nm), InGaAsP (1100 ~ 1670n)
m) A semiconductor laser using a material such as AlGaAsSb (1250 to 1400 nm). Irradiation of light to the color light-sensitive material in the present invention is performed by using the semiconductor laser described above or by using Nb: YAG crystal on GaAs _x P.
It may be a YAG laser (1064 nm) excited by a _(1-x) light emitting diode. Preferably 670,
It is preferable to select and use from among the light fluxes of the semiconductor lasers of 680, 750, 780, 810, 830 and 880 nm.

Further, in the present invention, the second harmonic generation element (SHG element) is for converting the wavelength of the laser light into one half by applying the non-linear optical effect. For example, the non-linear optical crystal. Examples include those using CD ^* A and KD ^* P (Laser Handbook, edited by Laser Society, published December 15, 1982, pages 122 to 1).
(See page 39). In addition, Li ⁺ is added to H in the LiNbO ₃ crystal.
A LiNbO ₃ optical waveguide element having an optical waveguide ion-exchanged with ⁺ can be used (NIKKEI ELECTRONIC
S 1986.7.14 (no.399) Nos. 89-90
page). The output device described in JP-A-63-226552 can be used in the present invention.

Photographic processing of a light-sensitive material produced by using the present invention is carried out, for example, by Research Disclosure (Resear).
ch Disclosure) 176, pp 28-30 (RD-17
Known photographic processing methods (color photographic processing) for forming dye images and processing solutions as described in 643) can be used. For details of a preferable example of the color development processing step and processing solution, see JP-A-2-248945.
No. 16 to 22.

[0114]

EXAMPLES Next, examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited thereto. Example 1 1000 ml of water, 25 g of deionized bone gelatin, 15 ml of 50% NH ₄ NO ₃ aqueous solution and 25% in a reaction vessel.
7.5 ml of NH ₄ aqueous solution was added and kept at 50 ° C., well stirred, 750 ml of 1N silver nitrate aqueous solution and 1N potassium bromide aqueous solution were added in 50 minutes, and the silver potential during the reaction was applied to the saturated sweet potato electrode. On the other hand, it was kept at +50 mV. The obtained silver bromide grains were cubic and had a side length of 0.76 ± 0.06 μm.
The temperature of the above emulsion was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the precipitate was washed with water for desalting. Next, 95 g of deionized bone gelatin and 430 ml of water were added to adjust the pH to 6.5 and pAg to 8.3 at 50 ° C., and then divided into 3 parts, each containing 4-hydroxy-5,6-propanol-1,3. , 3a, 7-
Tetrazaindene (Compound II-11) was added in an amount of 25 mg each, and then 36 mg each of the sensitizing dyes shown in Table 1 (corresponding to about 1.44 × 10 ^-6 mol per 1 m ^{2 of} silver bromide grain surface area).
Each was dissolved in methanol and added at 65 ° C. over 15 minutes. Then, it was aged at that temperature for 20 minutes. Subsequently, sodium thiosulfate, sodium chloroaurate and potassium thiocyanate were added to obtain the optimum sensitivity, and 60
Aged at 45 ° C. for 45 minutes. 0.74 in 1 kg of this emulsion
Molar silver bromide was included. 50 g each of these emulsions
One by one, and silver the precursor as shown in Table 1.
2.2 × 10 ⁻⁴ mol was added per mol. Then emulsion 5
10% gel of deionized gelatin per 0 g 15
g and 55 ml of water were added and coated on a cellulose triacetate film base as follows. Coating amount of the solution, the silver amount 2.5 g / m ^2, set so that the amount of gelatin 3.8 g / m ^2, so that the amount of gelatin 1.0 g / m ² in the upper layer, sodium dodecylbenzenesulfonate 0.22g
/ Liter, p-sulfostyrene sodium homopolymer 0.50 g / liter, 1,3-bis (vinylsulfonyl) -2-propanol 3.9 g / liter, and an aqueous solution containing gelatin 50 g / liter as the main components were simultaneously applied.

The prepared coated sample was measured for absorption spectrum using a spectrophotometer U-3410 manufactured by Hitachi, Ltd. with an integrating sphere, and was further spectrally exposed through a wedge using an isoenergy spectroscopic exposure machine. The exposed sample is D-72
After development, the development solution was stopped, fixed, washed with water and dried. Then, the sensitivities at the spectral sensitivity maximum wavelength, the spectral sensitivity maximum wavelength +30 nm, and the spectral sensitivity maximum wavelength -30 nm were obtained. The sensitivity was expressed by the reciprocal of the exposure amount required to give the fog density an optical density of 0.2. The sensitivity [S (max)] at the obtained spectral sensitivity maximum wavelength and 30 nm from the spectral sensitivity maximum wavelength
Ratio of sensitivity at short wavelength [S (-30nm)] to sensitivity at 30nm long wavelength [S (+ 30nm)], and absorbance at longest wavelength absorption maximum wavelength [Abs (max)] 30nm shorter than absorption maximum wavelength The ratio of the absorbance at wavelength [Abs (-30 nm)] to the absorbance at 30 nm long wavelength [Abs (+30 nm)] is shown in Table 1. Table 2 shows (1)
Immediately after coating, the results of (2) storage at 50 ° C. and 75% RH for 7 days, and (3) 6 months after natural storage were shown. Immediately after coating, the sensitivity of Sample 1-1 is 1
The sensitivity of the sample aged with a relative value of 00 is -30
The sensitivity of the same coated sample stored in a freezer at 0 ° C. for the same period was shown as a relative value when the sensitivity was 100.

[0116]

[Table 1]

[0117]

[Table 2]

[0118]

[Chemical 20]

Example 2 The silver halide emulsion used in Example 2 was prepared as follows. (1st liquid) Water 1000cc NaCl 4.65g Gelatin 22g Citric acid 0.80g (2nd liquid) KBr 25.3g NaCl 32.3g K ₂ IrCl ₆ (0.005%) 11.2cc Na ₃ RhCl ₆・ 2H ₂ O (10 ^-5 mol / l) 18.9 cc Water added 348 cc (3rd liquid) AgNO ₃ 120.6 g Water added 348 cc (4 liquid) KBr 30.0 g NaCl 48.7 g Water added 552 cc (5 liquid) ) AgNO ₃ 176.3 g Water was added to heat 552 cc (1st solution) to 50 ° C., and 262 cc of each of (2nd solution) and (3rd solution) was spent for 12 minutes and simultaneously added at a constant flow rate. After that, (4 solution) and (5 solution) were added simultaneously spending 20 minutes. After 10 minutes from the start of addition of (4 solution) and (5 solution) to the end of addition, the sensitizing dye (I-
11) A methanol solution containing 777 mg (corresponding to about 1.22 × 10 ^-6 mol / m ² of surface area of silver chlorobromide grains) was simultaneously added at a constant flow rate. Then lower the temperature,
A copolymer of isobutene and monosodium maleate was added as a flocculant, and the precipitate was washed with water for desalting. Add water and deionized bone gelatin, pH 6.1, pAg
Was adjusted to 7.5. Tetrazaindene compound (II-11) was added to this emulsion in an amount of 8 × 10 ^-4 mol per mol of silver. After ripening at 60 ° C. for 10 minutes, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added. , Optimally chemically sensitized. Average side length of particle size 0.28 μm,
Coefficient of variation (standard deviation divided by average side length: s / d)
A monodisperse cubic silver chlorobromide emulsion containing 0.08 and 30 mol% of silver bromide was prepared. Next, the sensitizing dye (I-11) added was changed to the sensitizing dye (I-18), and 825 mg of it was added, and a silver chlorobromide emulsion was separately prepared in the same manner as above. These emulsions were divided, and the precursors shown in Table 3 were added to each in an amount of 1.5 × 10 ^-5 mol per mol of silver, and further 4-hydroxy-6-methyl-per 1 kg of emulsion (containing 1 mol of silver). 0.65 g of 1,3,3a, 7-tetrazaindene, 280 g of 10% gel of deionized gelatin, 1.041 of water, and 7 g of 1,2-bis (vinylsulfonylacetylamino) ethane were added, and polyethylene was added. 1.2g silver on terephthalate film base
/ M ² was applied in the same manner as in Example 1.

The coated sample was developed by using a developing machine FD-800RA manufactured by Fuji Photo Film Co., Ltd. using a developer LD-835 manufactured by Fuji Photo Film Co., Ltd. at 38 ° C. for 20 seconds. In exactly the same manner as in Example 1, the absorption spectrum, the spectral sensitivity maximum wavelength, and the spectral sensitivity maximum wavelength −30.
nm and spectral sensitivity The sensitivity at the maximum wavelength + 30 nm is calculated respectively,
The results of the sensitivity ratio and the absorbance ratio are shown in Table 3. Table 4 shows
(1) Spectral sensitivity immediately after coating and (2) Six months after natural storage The results of sensitivity and fog at the maximum wavelength are shown. The sensitivity immediately after coating was a relative value with the sensitivity of Sample 2-1 being 100, and the sensitivity of the aged sample was 100 for the same coated sample stored in a freezer at -30 ° C for the same period. It was shown by the relative value of time.

[0121]

[Table 3]

[0122]

[Table 4]

Example 3 The silver halide emulsion used in Example 3 was prepared as follows. (1 liquid) Water 1000 cc NaCl 5.5 g Gelatin 32 g (2 liquid) Sulfuric acid (1N) 24 cc (3 liquid) 1% aqueous solution of 1,4-dimethylimidazolidine-5-thione 3 cc (4 liquid) NaCl 11.00 g water 200cc (5 solution) AgNO ₃ 32g Water added 200cc (6 solution) NaCl 44.05g K ₂ IrCl ₆ (0.001%) 4.54cc Water added 600cc (7 solution) AgNO ₃ 128cc water 600 cc (1 liquid) was heated to 56 ° C., and (2 liquid) and (3 liquid) were added. Then, (4 solution) and (5 solution) were added simultaneously spending 10 minutes. Further, after 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 20 minutes. Five minutes after the completion of the addition, the temperature was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the precipitate was washed with water for desalting. Add water and deionized bone gelatin and adjust pH to 6.
2. Monodispersed silver chloride cubic emulsion with pAg adjusted to 7.4, average side length of grain size of 0.54 μm, and coefficient of variation (standard deviation divided by average side length: s / d) of 0.09. Was prepared. This emulsion was divided into two parts, and each emulsion was added with 5 × 10 ^-4 mol of tetrazaindene compound (II-11) per mol of silver at 60 ° C., and after 5 minutes, a sensitizing dye (I-1
6) or (I-9) of 3.7 per mol of silver, respectively.
× 10 ^-4 mol was added (corresponding to about 1.29 × 10 ^-6 mol per 1 m ² of surface area of silver chloride grains). After aging for 30 minutes as it is, sodium thiosulfate is added to these emulsions,
After optimal chemical sensitization, tetrazaindene compound (II-11) was added again at 1 × 10 ⁻³ mol per mol of silver,
As shown in Table 5, 8 × 10 ⁻⁴ mol of the precursor was added. A polyethylene terephthalate film support was used as the support. The amount of coating liquid was set so that the amount of silver was 1.6 g / m ² and the amount of gelatin was 3.0 g / m ^2, and the upper layer consisted of
Dodecylbenzenesulfonic acid sodium salt 0.1 g, p-sulfostyrene sodium homopolymer 0.22 g / l, 2-hydroxy-4,6-dichloro-1,3,5-, so that the amount of gelatin will be 1.0 g / m ^2. An aqueous solution containing 3.1 g / liter of sodium salt of triazine and 50 g / liter of gelatin as main components was simultaneously applied.

For the coated sample, the absorption spectrum and the sensitivities at the spectral sensitivity maximum wavelength, the spectral sensitivity maximum wavelength −30 nm and the spectral sensitivity maximum wavelength +30 nm were obtained respectively in the same manner as in Example 1, and the sensitivity ratio and the absorbance ratio were obtained. The results are shown in Table 5. Table 6 shows the results of (1) immediately after coating and (2) after 6 months of natural storage, the spectral sensitivity at maximum wavelength and fog. The sensitivity immediately after coating is a relative value with the sensitivity of Sample 3-1 being 100, and the sensitivity of the aged sample is 10 times that of the same coated sample stored in a freezer at -30 ° C for the same period.
It is shown as a relative value when 0 is set.

[0125]

[Table 5]

[0126]

[Table 6]

Example 4 The silver halide emulsion used in Example 4 was prepared as follows. 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of a 1% aqueous solution of N, N′-dimethylimidazolidine-2-thione was added. An aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 15 μg of rhodium trichloride and 0.2 mol of sodium chloride were added and mixed at 56 ° C. with vigorous stirring. continue,
An aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added and mixed at 56 ° C. with vigorous stirring. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, an aqueous solution further containing 0.020 mol of silver nitrate, 0.015 mol of potassium bromide and 0.
40 ° C. with vigorous stirring with an aqueous solution containing 005 mol and 0.8 mg of potassium hexachloroiridium (IV) ate
And mixed in. After that, a polymer flocculant was added and sedimented, followed by desalting and washing with water. Then 4 x 10 per mole of silver
^-4 mol of tetrazaindene compound (II-11) and 3.8
^{X10 -4} mol of sensitizing dye (I-8) was added as a methanol solution at 60 ° C and ripened for 30 minutes. Then, 90.0 g of lime-processed gelatin and triethylthiourea were added, and the mixture was aged at 55 ° C. to obtain the maximum sensitivity and chemically sensitized, and then the tetrazaindene compound (II-1
1) was further added at 5.0 × 10 ⁻⁴ mol per mol of silver. The silver chlorobromide grains of the emulsion thus prepared were cubic with an average grain size of 0.52 μm (coefficient of variation 0.08). The grain size is represented by the diameter of a circle equivalent to the projected area of the grain, and the coefficient of variation is the standard deviation of the grain size divided by the average grain size.

Then, the halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from the silver halide crystals. Using the monochromatic CuK (α) ray as the radiation source (20
The diffraction angle was measured in detail from the 0) plane. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. The halogen composition of the silver halide constituting the crystal can be determined by calculating the lattice constant from the diffraction angle of the measured peak. The measurement results of the silver chlorobromide emulsion prepared as described above show that in addition to the main peak at 100% of silver chloride,
It has a center of 0 mol% (silver bromide 30 mol%) and silver chloride 6
It was possible to observe a broad diffraction pattern with a skirt around 0 mol% (silver bromide 40 mol%).

Next, using this emulsion, a paper support laminated on both sides with polyethylene was coated with a color coupler as shown below to prepare a sample. The coating liquid was prepared as follows. Yellow coupler (Ex-
Y) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-2) 1.4 g, and ethyl acetate 2
7.2 ml and 8.2 g of the solvent (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 8 ml of 10% aqueous dodecylbenzenesulfonic acid solution. The silver chlorobromide emulsion prepared above was added with 6 × 10 ⁻⁴ mol of precursor and the above emulsified dispersion per mol of silver at 40 ° C. as shown in Table 7 and dissolved and mixed. A coating solution was prepared so that the composition was obtained. A protective layer was provided on the upper layer, and a sodium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine was used as a gelatin hardening agent for each layer. The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. <Support> Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)] <Silver chlorobromide emulsion layer (yellow color forming layer)> The silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (Ex-Y) 0.82 Color image stabilizer (Cpd-1) 0.19 Color image stabilizer (Cpd-2) 0.06 Solvent (Solv-1) 0.35 <Upper layer (protective layer)> Gelatin 1.33 Polyvinyl alcohol Acrylic modified copolymer 0.17 (Modification degree 17%) Liquid paraffin 0.03

[0130]

[Chemical 21]

The reflection absorption spectrum of the coated sample prepared was measured in the same manner as in Example 1. Spectral sensitivity was also exposed in the same manner as in Example 1, and the sensitivity was determined. The developing treatment was the color developing treatment described in the above example, and the sensitivity was the exposure required to give a fog density of 0.5 coloring density. Expressed as the reciprocal of the quantity.
Table 7 shows the results of the obtained sensitivity ratio and absorbance ratio. Table 8 shows the results of (1) immediately after coating and (2) after 6 months of natural storage, the spectral sensitivity at maximum wavelength and fog. The sensitivity immediately after coating was a relative value with the sensitivity of Sample 3-1 being 100, and the sensitivity of the aged sample was 100 for each of the same coated samples stored in a freezer at -30 ° C for the same period. It was shown by the relative value of time.

[0132]

[Table 7]

[0133]

[Table 8]

The inventors of the present invention first described in Japanese Patent Application No. 4-91,43.
As disclosed in No. 7, when the J band sensitization was performed even in the infrared region, the spectral sensitivity and the storage stability were dramatically improved as compared with the conventional molecular band sensitization. As is clear from the results of Table 2, Table 4, Table 6 and Table 8 shown in the examples, the comparative sample containing the conventionally well-used compound lowers the sensitivity immediately after coating, and after storage The sample of the present invention maintained high sensitivity not only after coating but also after storage.

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

[Procedure amendment]

[Submission date] September 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, potassium salt, rhenium salt, ruthenium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or You may make the complex salt etc. coexist. Particularly, rhenium salt, iridium salt, rhodium salt, or iron salt is more preferable. As the addition amount of these, any amount can be added as necessary. For example, iridium salts (for example, Na ₃ IrCl ₆ , Na ₂ Ir
_{Cl 6, Na 3 Ir (CN} ) 6 , etc.), per mol of silver 1 × 10 ^-8 or more, an amount in the range of 1 × 10 ^-5 or less, rhodium salts _{(e.g., RhCl 3, K 3 Rh (} CN ) ₆ etc.) is 1 × 10 per mol of silver.
An amount in the range of ^-8 to 1 × 10 ^-6 is desirable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

The interface between the localized phase having a high silver bromide content and the other phase may have a clear phase boundary, or may have a short transition region in which the halogen composition gradually changes. You can do it. In order to form such a localized phase having a high silver bromide content, various methods can be used. For example, a soluble silver salt and a soluble halogen salt can be reacted by a one-sided mixing method or a simultaneous mixing method to form a localized phase. Further, the localized phase can be formed by using a so-called conversion method including a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, the localized phase can be formed by adding fine silver bromide particles and recrystallizing them on the surface of the silver chloride particles.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0108

[Correction method] Change

[Correction content]

[0108]

[Equation 1]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0119

[Correction method] Change

[Correction content]

Example 2 The silver halide emulsion used in Example 2 was prepared as follows. (1st liquid) Water 1000cc NaCl 4.65g Gelatin 22g Citric acid 0.80g (2nd liquid) KBr 25.3g NaCl 32.3g K ₂ IrCl ₆ (0.005%) 11.2cc Na ₃ RhCl ₆・ 2H ₂ O (10 ^-5 mol / l) 18.9 cc Water added 348 cc (3rd liquid) AgNO ₃ 120.6 g Water added 348 cc (4 liquid) KBr 30.0 g NaCl 48.7 g Water added 552 cc (5 liquid) ) AgNO ₃ 176.3 g Water was added to heat 552 cc (1st solution) to 50 ° C., and 262 cc of each of (2nd solution) and (3rd solution) was spent for 12 minutes and simultaneously added at a constant flow rate. After that, (4 solution) and (5 solution) were added simultaneously spending 20 minutes. After 10 minutes from the start of addition of (4 solution) and (5 solution) to the end of addition, the sensitizing dye (I-
11) A methanol solution containing 777 mg (corresponding to about 1.22 × 10 ^-6 mol / m ² of surface area of silver chlorobromide grains) was simultaneously added at a constant flow rate. Then lower the temperature,
A copolymer of isobutene and monosodium maleate was added as a flocculant, and the precipitate was washed with water for desalting. Add water and deionized bone gelatin, pH 6.1, pAg
Was adjusted to 7.5. Tetrazaindene compound (II-11) was added to this emulsion in an amount of 8 × 10 ^-4 mol per mol of silver. After ripening at 60 ° C. for 10 minutes, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added. , Optimally chemically sensitized. Average side length of particle size 0.28 μm,
Coefficient of variation (standard deviation divided by average side length: s / d)
A monodisperse cubic silver chlorobromide emulsion containing 0.08 and 30 mol% of silver bromide was prepared. Next, the sensitizing dye (I-11) added was changed to the sensitizing dye (I-18), and 825 mg of it was added, and a silver chlorobromide emulsion was separately prepared in the same manner as above. These emulsions were divided, and the precursors shown in Table 3 were added to each in an amount of 1.5 × 10 ^-3 mol per mol of silver, and further 4-hydroxy-6-methyl-per kg of the emulsion (containing 1 mol of silver). 0.63 g of 1,3,3a, 7-tetrazaindene, 280 g of 10% gel of deionized gelatin, 1.041 of water, and 7 g of 1,2-bis (vinylsulfonylacetylamino) ethane were added, and polyethylene was added. 1.2g silver on terephthalate film base
/ M ² was applied in the same manner as in Example 1.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a support and at least one silver halide photographic emulsion layer, wherein at least one of the silver halide emulsion layers is a polarographic half-wave reduction potential for a saturated calomel electrode. Is -1.
At least one spectral sensitizer less base than 25V and having a polarographic half-wave oxidation potential no less than 0.38V
Contains a silver halide emulsion spectrally sensitized with a seed, and the silver halide emulsion layer has a sensitization maximum at a wavelength longer than 730 nm, and the spectral sensitizer provides a sensitivity at this spectral sensitivity maximum wavelength. Is spectrally sensitized so that it is 4.5 times or more of the spectral sensitivity for light having a wavelength of 30 nm longer than the maximum wavelength of the spectral sensitivity, and 2 times or more of spectral sensitivity for light of 30 nm shorter than the wavelength of the maximum spectral sensitivity. And at least one of the silver halide emulsion layers and / or other hydrophilic colloid layers contains at least one precursor of a photographically useful reagent. 2. The silver halide light-sensitive material according to claim 1, wherein at least one of the spectral sensitizers used is a dicarbocyanine dye represented by the following general formula (I). General formula (I) In the formula, Z ₁ and Z ₂ may be the same or different,
Represents a sulfur atom or a selenium atom. Y ₁ and Y ₄ represent a hydrogen atom, and Y ₁ when Y ₂ is not a hydrogen atom and Y ₄ when Y ₅ is not a hydrogen atom also represent a methyl group, an ethyl group, a hydroxy group or a methoxy group. Y ₂ , Y
₃ , Y ₅ and Y ₆ are hydrogen atoms, optionally substituted alkyl groups having 3 or less carbon atoms, halogen atoms, hydroxy groups, methoxy groups, ethoxy groups, methylthio groups, ethylthio groups, monocyclic aryl groups, acetyl In addition to representing an amino group and a propionylamino group, Y ₂ is linked to Y ₁ or Y ₃ and Y ₅ is linked to Y ₄ or Y ₆ to form a methylenedioxy group, trimethylene group, tetramethylene group or tetradehydro group. It also represents a tetramethylene group. R ₁ and R ₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group. R ₃ and R
₅ represents a hydrogen atom, R ₃ is R ₁ and R ₅ is R
Represents that ₂ and each can be connected to form a 5-membered ring or a 6-membered ring. R ₄ represents a hydrogen atom or an optionally substituted lower alkyl group. R ₆ represents a hydrogen atom, a methyl group, an ethyl group or a propyl group, and R ₇ represents an optionally substituted lower alkyl group or an optionally substituted phenyl group. X represents a counter ion necessary for neutralizing the charge. n represents 0 or 1, and is 0 in the case of an intramolecular salt. 3. The silver halide emulsion layer according to claim 1, wherein at least a part of the silver halide grains contained in the silver halide emulsion layer comprises at least one tetrazaindene compound and at least one spectral sensitizer. A silver halide light-sensitive material characterized by being chemically sensitized in the presence.