JPH06342192A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having spectral sensitivity and appropriate sensitivity characteristics to the laser imager of 810 to 840nm and also processability with the automatic developing device by providing a specific photosensitive silver halide emulsion layer on one side of a transparent substrate and a hydrophilic colloidal layer contg. a specific dye on the other side of the substrate. CONSTITUTION:One side of the transparent substrate is provided with the photosensitive silver halide emulsion layer, which has a <=2.8 g/m<2> silver coating amount and a <=3.5g/m<2> total gelatin coating amount together with the protective layer and the silver halide emulsion in which is spectrally sensitized in the 810 to 840nm wavelength region with the spectrally sensitizing dye represented by the formula I. The other side of the transparent substrate is provided with the hydrophilic colloidal layer contg. the dye represented by the formula III, etc. processing is performed in <=45 sec Dry to Dry time by using the automatic developing device. In the formulas I and II, each of Z5 and Z6 is a five or six membered nitrogen heterocycle; Q5 is an atomic group forming five to seven membered rings respectively; each of R4 and R5 is an alkyl group; each of L32 to L40 is a methine group; each of Y<1> and Y<2> is a chalcogen atom, etc.; each of Z<1> and Z<2> is a nonmetallic, atomic group for forming a benzo- or naphto condensed ring; each of R<1> and R<2> is an alkyl group; L is a methine group.

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 exposed by an infrared laser light source, and more particularly to an infrared sensitive material having suitability for rapid processing.

[0002]

2. Description of the Related Art Recently, in the medical field, X-ray CT, MRI
2. Description of the Related Art As an image recording system for a diagnostic device such as (nuclear magnetic resonance device), a laser imager which scans a laser beam and records it on a photographic light-sensitive material has been widely used. It is desired that this laser imager system be recorded and developed in a shorter time for quick diagnosis. The recording laser of the laser imager is He-N
There are e-lasers and semiconductor lasers.

The exposure wavelength of the laser imager is 600 to 700 nm for He-Ne laser, AlCaP (semiconductor) laser, etc., and 750 to 850 nm for semiconductor.
Some are in the infrared region. Of these, 750 to 850 nm
Since the semiconductor laser imager with the exposure wavelength is inexpensive and stable and has a merit that the optical system can be made cheaper and more compact than that of the He-Ne laser, it has become popular and is the mainstream in the market. Is expected to become.

Various characteristics are required for the light-sensitive materials used in these laser imagers, but in particular 10 ⁻³
Since exposure is performed in a short time of about 10 ⁻⁷ seconds, high sensitivity is an essential condition even under such conditions.

Further, it is known that the output image from the laser imager has adjacent portions in the image where the difference in density is clearly different, and that portion causes unevenness in processing when rapidly processed by an automatic developing machine. ing. This can be improved by accelerating the development progress of the light-sensitive material, and therefore it is necessary for the light-sensitive material to have a small sensitivity variation with the development time. In addition, it is necessary to use a dye suitable for the wavelength of the light source in order to prevent anti-halation or irradiation in a portion where there is a clear difference in density.

On the other hand, in order to achieve rapid processing, it is necessary to have a light-sensitive material that gives a sufficient blackening density in a short time, and a property that fixing, washing and drying are completed in a short time. In particular, various methods for rapidly completing the drying have been studied so far, but as a method often used to improve the drying property of a light-sensitive material, a sufficient amount of a hard material is previously prepared in the step of applying the light-sensitive material. A method of reducing the water content of the dry initiator in the photosensitive material by adding a filming agent (gelatin cross-linking agent) in advance to reduce the swelling amount of the emulsion layer or surface protective layer in the developing, fixing and washing steps. is there. This method can shorten the drying time by using a large amount of a hardener, but the swelling becomes small. As a result, the development is delayed, the soft feeling becomes low and the covering power is lowered. Further, a method for rapid high-temperature processing with a processing agent in which the developing solution and the fixing solution do not substantially have a gelatin hardening effect is disclosed in, for example, JP-A-63-1.
36043 and the like. These methods are not sufficiently effective methods because they accelerate development progress and improve fixability, but eventually slow dryness.

On the other hand, as a method of accelerating the development and increasing the covering power, it is known to use various additives to silver halide. For example, polyacrylamides may be used as polymers in US Pat. No. 3,271,158.
Issue No. 3,514,289 Issue No. 3,514,28
No. 9, etc., and dextran compounds as sugars are disclosed in US Pat. Nos. 3,063,838 and 3,272,631. However, if these compounds are used in an amount sufficient to achieve their purpose, they have the drawbacks of slow drying and poor film strength. Further, it is preferable that the antihalation or irradiation prevention dye for improving the image quality is decomposed during rapid processing or is eluted and flowed out of the system. Further, the spectral sensitizing dye is required to have high sensitivity and to have no residual color in rapid processing.

Further, from the viewpoint of rapid processing, further enhancement of the sensitivity of the light-sensitive material and improvement of the covering power are issues that have been continuously pursued. Generally, the covering power is lowered if the sensitization is realized by increasing the particle size.
It is necessary to reduce the load on the developing solution and the fixing solution by achieving higher sensitization with the particles of the same size, or by achieving higher covering power with the same sensitivity and lowering the coating silver amount. It is also important to compensate the decrease in sensitivity due to the decrease in grain size with a sensitizing dye. The color tone of medical images is
is important. Temperature control type is difficult to diagnose and is not preferred.
Particular caution is required when reducing the grain size and when the halogen composition of the silver halide emulsion is based on silver chlorobromide.

Thus, the optical system is inexpensive, compact, and
As a popular photographic light-sensitive material for laser imagers with an exposure range of 750 to 850 nm, it has high sensitivity, high covering power, excellent development progress, and rapid processing suitability containing a sensitizing dye or dye with little residual color. Photographic materials have been desired.

[0010]

The object of the present invention is 81
It is an object of the present invention to provide a silver halide light-sensitive material having spectral sensitivity and sensitivity suitability for a laser imager having a laser light source of 0 to 840 nm and suitability for dry-to-dry processing for 45 seconds or less in an automatic processor.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to have a photosensitive silver halide emulsion layer on one side of a transparent support, and the silver halide emulsion layer has a coated silver amount of 2.8 g / m 2. ² or less, the coating amount of gelatin including the protective layer is 3.5 g / m ² or less, and the silver halide emulsion is a spectral sensitizing dye represented by the general formula [I] and is spectrally sensitized in the wavelength range of 810 to 840 nm. Of the general formulas [IIa], [IIb], [II] for preventing the above-mentioned spectral sensitized region from being antihalation or irradiation in at least one of the hydrophilic colloid layers on the other side of the support.
It was found to be achieved by an infrared-sensitive rapid processing silver halide light-sensitive material containing at least one dye represented by c] and processed in an automatic processor in a dry to dry time of 45 seconds or less. The halogen composition of the silver halide emulsion is preferably achieved by setting the silver chloride content to 10 mol% or more and 50 mol% or less. Even more preferably, the iridium compound is contained in the silver halide emulsion. The present invention is particularly useful when used as a silver halide light-sensitive material for medical laser imagers having a semiconductor laser light source of 810 to 840 nm.

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

In the general formula [I], Z ₅ and Z ₆ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Q ₅ represents an atomic group necessary for forming a 5-, 6- or 7-membered ring. R _4, R ₅ represents an alkyl group.
L ₃₂ , L ₃₃ , L ₃₄ , L ₃₅ , L ₃₆ , L ₃₇ , L ₃₈ , L ₃₉ , L
₄₀ represents a methine group or a substituted methine group. Further, it may form a ring with another methine group, or may form a ring with an auxochrome. n ₈ and n ₉ represent 0 or 1. M ₅ represents a charge neutralizing counterion, and m ₅ is a number of 0 or more necessary for neutralizing the charge in the molecule.

Next, the general formula [I] will be described in detail. R ₄ and R ₅ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or substituted alkyl groups (eg, as a substituent,
Carboxy group, sulfo group, cyano group, halogen atom (for example, fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), Alkoxy groups having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), monocyclic aryloxy groups having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), acyloxy groups having 3 or less carbon atoms (eg, Acetyloxy, propionyloxy), acyl groups having 8 or less carbon atoms (eg acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (eg carbamoyl, N, N-).
Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group having 10 or less carbon atoms (eg, phenyl, 4-chloro) Phenyl,
4-methylphenyl, α-naphthyl) -substituted alkyl groups having 18 or less carbon atoms}. Preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (eg, 2-carboxyethyl group, carboxymethyl group) ), And a sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group).

M ₅ m ₅ is included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye.
Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be either an inorganic or organic anion, for example a halogen anion (eg a fluoride ion, Chloride ion, bromine ion, iodine ion), substituted aryl sulfonate ion (eg p-
Toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate Examples thereof include ions (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate salt, acetate ion, and trifluoromethanesulfonate ion. Of these, ammonium ion, iodine ion and p-toluenesulfonate ion are preferable.

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

The nucleus formed by Z ₅ and Z ₆ is preferably a benzothiazole nucleus, a naphthothiazole nucleus,
They are a benzoxazole nucleus, a naphthoxazole nucleus, and a benzimidazole nucleus.

L ₃₂ , L ₃₃ , L ₃₄ , L ₃₅ , L ₃₆ , L ₃₇ , L
₃₈ , L ₃₉ and L ₄₀ are methine groups or substituted methine groups (eg, substituted or unsubstituted alkyl groups (eg, methyl group, ethyl group, 2-carboxyethyl group), substituted or unsubstituted aryl groups (eg, phenyl group) , O-carboxyphenyl group), heterocyclic group (eg barbituric acid), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy group, ethoxy group), amino group (eg N, N-diphenyl group) Amino group, N-methyl-N-phenylamino group, N-methylpiperazino group), alkylthio group (eg, methylthio group, ethylthio group), and the like}, and other methine groups and rings. It may be formed, or a ring may be formed with the auxiliary chromophore.

L ₃₄ is preferably an unsubstituted methine group, an unsubstituted alkyl group (eg methyl), an alkoxy group (eg methoxy), an amino group (eg N, N-).
Diphenylamino), a methine group substituted with a halogen atom (for example, chlorine) or a methine group substituted with a so-called acidic nucleus. The other L is preferably an unsubstituted methine group.

Specific examples of the sensitizing dye represented by the general formula [I] are shown below, but the scope of the present invention is not limited to these.

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

In order to achieve the present invention, the general formula [IIa],
Details of the dyes represented by [IIb] and [IIc] will be described. In the general formula [IIa], Y ¹ and Y ² are each a chalcogen atom, a —CH═CH— group, a —N (R ¹⁰ ) — group (R ¹⁰ represents an alkyl group), or a —C (R ¹⁰ ). (R
¹¹ ) -group (R ¹⁰ and R ¹¹ each represent an alkyl group), and Z ¹ and Z ² represent a non-metal atom group necessary for forming a benzo-condensed ring or a naphtho-condensed ring. R ¹ and R ² each represent an alkyl group, L may be the same or different and each represents a methine group, and at least one L is —OR ¹²
Group (R ¹² represents an alkyl group or an aryl group substituted with an acidic substituent), —N (R ¹² ) (R ¹³ ) group (R ¹² is the same as defined above, R ¹³ is a hydrogen atom or an acidic substituent) Represents an alkyl group or an aryl group substituted with), -SR ¹²
A group (R ¹² is as defined above) or —CH (R ¹⁴ ) (R ¹⁵ ).
A group (R ¹⁴ and R ¹⁵ each represent a cyano group, a carboxylic acid group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, provided that at least one of R ^{14 and} R ¹⁵ is An acidic substituent is included), X represents an anion, p represents 0 or 1, and
r is 0 or 1, m is 2 or 3, n is 1 or 2
Represents N is 1 when the dye forms an inner salt. However, it is assumed that the dye molecule has at least three acidic substituents.

The general formula [IIa] will be described in detail. Y
^The chalcogen atom represented by ¹ and Y ² is oxygen,
Examples include sulfur, selenium, and tellurium atoms. R ¹⁰ and R ¹¹ may be the same or different and each represents a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n
-Butyl group, n-pentyl group, etc.) and may have a substituent such as a sulfonic acid group, a carboxylic acid group, and a hydroxyl group.

R ¹ and R ² have the same meaning as the above-mentioned alkyl group, and further have a sulfonic acid group or a carboxylic acid group and an alkyl group having 1 to 5 carbon atoms (for example, 3-sulfopropyl group, 4-sulfobutyl group). , 2-carboxyethyl group, etc.)
Is preferred. In the present invention, the acidic substituent represents a sulfonic acid group, a carboxylic acid group or a phosphonic acid group, the sulfonic acid group is a sulfo group or a salt thereof, the carboxylic acid group is a carboxyl group or a salt thereof, a phosphonic acid The group means a phosphono group or a salt thereof, respectively. Examples of salts include alkali metal salts such as Na and K, ammonium salts, organic ethyl ammonium salts such as triethylammonium, tributylammonium, pyridinium and tetrabutylammonium.

Z¹And Z²According to the non-metal atomic group represented by
The benzo-condensed ring or naphtho-condensed ring formed by
Rogen atom (eg Cl, F, Br), substituted amino group
{For example, a dimethylamino group, a diethylamino group, a diamino
(4-sulfobutyl) amino group, di (2-carboxyene)
Cyl) amino group, etc.}, hydroxyl group, sulfonic acid group, carbo
An acid group or a ring directly or through a divalent linking group
Substituted or unsubstituted alkyl having 1 to 5 carbon atoms
Groups, {eg, methyl, ethyl, propyl, etc.
(As a substituent, sulfonic acid group, carboxylic acid group, hydroxyl group
Is preferred)} and the like. Bivalent string
The linking group is, for example, -O-, -NHCO-, -NHSO.
₂-, -NHCO₂, -NHCONH-, -COO-,
-CO-, -SO ₂And the like are preferable. More preferably,
Benzo substituted with sulfonic acid groups or carboxylic acid groups
Or is a naphtho-fused ring.

The alkyl group represented by R ^{12 of} L is a C 1-5 alkyl group having a sulfonic acid group or a carboxylic acid group (for example, carboxymethyl group, 2-carboxyethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.). The aryl group is preferably a phenyl group or a naphthyl group, which is substituted with a sulfonic acid group or a carboxylic acid group, and further an alkyl group (as defined above),
It may be substituted with a halogen atom (F, Cl, Br), a hydroxy group, or an amino group (which may be substituted with an alkylcarbonyl group or an arylcarbonyl group which has the same meaning as the above-mentioned substituted amino group or which will be described later).

The alkyl group and aryl group represented by R ^{13 of} L have the same meanings as the alkyl group and aryl group described for R ¹² . The acyl group represented by R ¹⁴ and R ^{15 of} L is R
^The alkyl moiety described in ¹⁰ and the aryl moiety described in R ¹² are included. The alkyl part of the alkoxycarbonyl group represented by R ¹⁴ and R ^{15 of} L has the same meaning as the alkyl group of R ¹⁰ , and the aryl part of the aryloxycarbonyl group has the same meaning as the aryl group of R ¹² . The carbamoyl group, sulfonyl group, and sulfamoyl group represented by R ¹⁴ and R ^{15 of} L may be substituted with the alkyl group described for R ¹⁰ or the aryl group described for R ¹² .

At least one of R ^{14 and} R ¹⁵ is substituted with an acidic substituent and further contains at least 3 acidic substituents in the dye molecule.

More preferably, it can be achieved by a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one dye represented by the formula [IIb].

In the general formula [IIb], Z¹And Z²Is
Non-necessary to form a benzo- or naphtho-fused ring
Represents a group of metal atoms. R¹, R², R³, R^Four, R^FiveOver
And R ⁶Each represents an alkyl group, and L is the same or different.
May represent a methine group, and at least one L is
-OR¹²Group (R¹²Is an alkyl substituted with an acidic substituent
Group or aryl group, where "substituted ari"
Group "), -N (R¹²) (R¹³) Group (R
¹²Is as defined above, R¹³Is a hydrogen atom or an acidic substituent
A substituted alkyl group or aryl group), -S
R¹²Group (R¹²Is as defined above) or -CH (R¹⁴) (R
¹⁵) Group (R¹⁴And R¹⁵Are cyano group, carboxylic acid group,
Acyl group, alkoxycarbonyl group, aryloxy group
Rubonyl group, carbamoyl group, sulfonyl group or sulfone group
Represents a famoyl group. However, R¹⁴Or R¹⁵At least
The other one contains an acidic substituent. ) Was replaced by
Represents a methine group, X represents an anion, m is 2 or 3
And n represents 1 or 2. Dye forms inner salt
Then n is 1. However, at least 4 in the dye molecule
Individual acidic substituents.

Each substituent in the general formula [IIb] has the same meaning as in the general formula [IIa]. However, the alkyl group of R ^{3 to} R ^{6 has} the same meaning as the alkyl group described for R ¹⁰ .

Further, it can be achieved by a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one dye represented by the formula [IIc].

In the general formula [IIc], Z¹And Z²Is
Non-necessary to form a benzo- or naphtho-fused ring
Represents a group of metal atoms. R¹, R², R³, R^Four, R^Fiveas well as
R⁶Each represents an alkyl group, R⁷And R⁸Is a hydrogen atom
Or a non-metal source necessary to form a 5- or 6-membered ring together
Represents the child group, R⁸Is -OR¹²Group (R¹²Is an acidic substituent
Represents a substituted alkyl group or aryl group), -N
(R¹²) (R¹³) Group (R ¹²Is as defined above, R¹³Is hydrogen
Or an alkyl group or an alkyl group substituted with an acidic substituent.
Represents a reel group), -SR¹²Group (R¹²Is synonymous with the above)
Or -CH (R¹⁴) (R¹⁵) Group (R¹⁴And R¹⁵Are each
Ano group, carboxylic acid group, acyl group, alkoxycarbonyl group
Group, aryloxycarbonyl group, carbamoyl group,
Represents a sulfonyl group or a sulfamoyl group. However, R
¹⁴Or R¹⁵At least one of which contains an acidic substituent
And X is an anion, and n is 1 or 2
Represents N is 1 when the dye forms an inner salt
It However, at least four acidic substituents must be present in the dye molecule.
Shall be included.

The substituent of the general formula [IIc] is represented by the general formula [IIa].
Is synonymous with.

Further, in the general formula [IIc], R ⁸ is —O.
R ¹⁶ (R ¹⁶ represents an alkyl group or an aryl group substituted with a sulfonic acid group or a carboxylic acid group), R
^This can be achieved by a silver halide photographic light-sensitive material containing a dye in which ⁷ and R ⁹ form a 5- or 6-membered ring with each other.

The alkyl group and aryl group of R ^{16 have} the same meaning as the alkyl group and aryl group described for R ¹² .

Specific examples of the present invention are shown below, but the scope of the present invention is not limited to these.

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

The dyes of the above [IIa] to [IIc] are dissolved in a suitable solvent [eg water, alcohol (eg methanol, ethanol etc.) methyl cellosolve, etc., or a mixed solvent thereof] or as an aqueous decomposition product. Preferably, it is added to the photosensitive or non-photosensitive hydrophilic colloid layer coating liquid. These dyes can be used in combination of two or more kinds. The amount of the above dye used is generally 10
^{-3 g / m 2 ~2.5g / m} 2, in particular 10 ^-3 g / m ² ~1.0g
A preferred amount can be found in the range of / m ² .

The photographic dyes represented by the above formulas [IIa] to [IIc] are particularly effective for the purpose of preventing irradiation, and when used for this purpose, they are mainly added to the emulsion layer. The photographic dyes represented by the general formulas [IIa] to [IIc] are also particularly effective as a dye for preventing halation,
In this case, it is added to the back surface of the support or a layer between the support and the emulsion layer. The photographic dyes represented by the general formulas [IIa] to [IIc] can be advantageously used also as filter dyes.

In the present invention, the dyes represented by the general formulas [IIa] to [IIc] are preferably used together with the binder.
The hydrophilic colloid material used as the binder includes
Gelatin, gelatin substitutes, collodion, gum arabic, alkyl esters of carboxylated cellulose, cellulose ester derivatives such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, Clavier, published August 16, 1960.
Synthetic resins such as the amphoteric copolymers described in US Pat. No. 2,949,442, polyvinyl alcohol and other materials well known in the art. Examples of polymeric gelatin substitutes include copolymers of allylamine and methacrylic acid, copolymers of allylamine and acrylic acid and acrylamide, hydrolyzed copolymers of allylamine and methacrylic acid and vinyl acetate, copolymers of allylamine and acrylic acid and styrene, Examples include copolymers of allylamine, methacrylic acid, and acrylonitrile.

The photosensitive silver halide used in the present invention is a silver halide composed of chlorine, bromine and / or iodide such as silver chlorobromide and silver chloroiodobromide. In this case, silver iodide is 0 to 3 mol%, preferably 0 to 1 mol%.
And silver chloride is 10 to 50 mol%, preferably 15 to
It is 40 mol%. In the case of silver chlorobromide, the silver chloride content is 10 to 50 mol%, preferably 15 to 40 mol%. Further, the silver halide grains (10
The ratio of (0) plane / (111) plane is preferably 3 or more, particularly preferably 4 or more, and further preferably 5 or more. The above ratio may be 100% on the (100) plane. (1
The silver halide grains having a (00) face / (111) face ratio of 3 or more, preferably 5 or more are preferably contained in an amount of 50 wt% or more, and particularly preferably 80 wt% or more.
The silver halide grains having a (100) face / (111) face ratio of 3 or more according to the present invention can be prepared by various methods. The most common method is to keep the pAg value during grain formation at a constant value of 8.1 or less, and simultaneously add the silver nitrate aqueous solution and the alkali halide aqueous solution at a rate higher than the dissolution rate of the particles and at a rate at which re-nucleation does not occur. There is (so-called control double jet method). The pAg value is more preferably 7.8 or less, and further preferably 7.6 or less. There is no particular limitation on the pAg value during nucleation of silver halide, but the pAg value during grain growth is 8.1 or less, preferably 7.8 or less, and more preferably 7.6 or less. Also,
The method of reacting the aqueous solution of silver nitrate and the aqueous solution of alkali halide may be a one-sided mixing method, but the simultaneous mixing method is preferable to obtain good monodispersity. These emulsions may be coarse grains, fine grains or mixed grains thereof, but preferably have an average grain size (measured by, for example, a projection photographing method or a number average method) of about 0.1 to 0.7 µ, more preferably 0. It is preferable to use emulsion particles having a grain size of 15 μm to 0.5 μm.

Grain formation is preferably cubic, but tabular grains having a spherical shape, a potato shape, a plate shape, and an aspect ratio of 5 or more (specifically, Research Disclosure Item No. 22534
P. 20-p. 58)) and an irregular crystal form. These light-sensitive silver halide emulsions may be mixed with a substantially non-light-sensitive silver halide emulsion (eg, internally fogged fine grain emulsion). Of course, emulsions having different grain sizes, halogen compositions, etc. may be separately coated in different layers to increase the exposure latitude. A narrow so-called monodisperse particle size distribution is preferably used. More specifically, as a monodisperse emulsion, 90% or more of all grains within ± 40% of the average grain size, preferably 9% of all grains within ± 20%.
An emulsion containing 0% or more is preferable. Furthermore, even if the crystal structure of the silver halide grains is uniform to the inside,
Also, a layered structure in which the inside and the outside are different, British Patent No. 635,841 and US Patent No. 3,622,318.
As described above, it may be a so-called conversion type, or may be a type that forms a latent image mainly on the surface or an internal latent image type that is formed inside the grain.

The photographic material of the present invention may not contain iridium ions, but it is preferable to contain iridium ions in an amount of 10 ^-8 mol or more per mol of silver halide (per mol of silver). To contain iridium ions, a water-soluble iridium compound (for example, hexachloroiridium (III) salt) should be added when preparing a silver halide emulsion.
Is usually added in the form of an aqueous solution. It may be added in the form of the same aqueous solution as the halide for grain formation, may be added before grain formation, during grain formation, or after grain formation until chemical sensitization, but is particularly preferable. Is addition at the time of grain formation. The iridium ion is preferably used in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of silver halide (silver 1 mol), more preferably 5 × 10 ^-8 〜.
It is 5 × 10 ⁻⁷ mol.

When the silver halide grains are formed, as a silver halide solvent for controlling the growth of the grains, for example, ammonia, rhodancali, rhodanammon, and a thioether compound (for example, US Pat. No. 3,271,15).
No. 6, No. 3,574,628, No. 3,704,1
No. 30, No. 4,297,439, No. 4,276,
374) and thione compounds (for example, JP-A-53-1).
44,319, 53-82,408, 55.
-77,737, etc.), amine compounds (for example, JP-A-54-100,717, etc.) and the like can be used. In addition to the silver halide solvent, a compound that is adsorbed on the grain surface to control the crystal habit, such as a cyanine sensitizing dye, a tetrazaindene compound, or a mercapto compound, can be used during grain formation.

The emulsion used in the present invention can be chemically sensitized by other methods commonly used, for example, sulfur sensitization (US Pat. Nos. 1,574,944 and 2,278,947).
No. 3,021,215, No. 3,635,71
No. 7, etc.), reduction sensitization (US Pat. No. 2,518,698)
Issue, Research Disclosur
e) Vol. 176 (1978.12) 17643, item 3, etc.) and sensitization with thioether compounds (for example, US Pat. Nos. 2,521,926 and 3,021,215).
No. 3,046,133, No. 3,165,55
No. 2, No. 3,625,697, No. 3,635,7
No. 17, No. 4,198,240, etc.), a sensitizing method using a selenium compound, a tellurium compound, or various sensitizing methods obtained by compounding them. Examples of the sensitizer used in combination include reduction sensitizers such as tin chloride, phenylhydrazine and reductone. The silver halide emulsion of the present invention is better than sulfur thiosulfate and is preferably chemically sensitized with sulfur.
For example, the thiosulfate is preferably an alkali thiosulfate such as sodium thiosulfate or potassium thiosulfate. The amount of thiosulfate used in the present invention is 0.1 to 10 per mol of silver.
It is preferably mg, particularly 0.5 to 5 mg.

Furthermore, it is preferable to use gold sensitization (for example, US Pat. Nos. 2,540,085 and 2,399,083) in the emulsion used in the present invention. As a specific gold sensitizer, potassium chloroaurate,
There are aura thiosulfate and potassium chloroparadate. These gold compounds may be added before or after the sulfur sensitizer. It can also be added at the same time as the sulfur sensitizer. The amount of the gold sensitizer used in the present invention is 10 ^-7 to 10 ^-3 per mol of silver halide.
It is preferably used in a molar ratio, and further 10 ⁻⁶ to 10
^It is particularly preferable to use it at a ratio of ^-4 mol.

The above-mentioned spectral sensitizing dye used in the present invention is a silver halide in a ratio of 10 ^-6 to 10 ^-3 mol, preferably 5 × 10 ^{-6 to} 5 × 10 ^-4 mol, per mol of silver halide. It is contained in a photographic emulsion. The spectral sensitizing dyes used in the present invention can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Although the dye is usually added after chemical sensitization in many cases, it may be added during grain formation or before chemical sensitization. It is also possible to use ultrasonic waves for dissolution. US Pat. No. 2,912,343 for addition to emulsions.
No. 3,342,605, No. 2,996,28
The methods described in No. 7, No. 3,429,835 and the like are also used. The above-mentioned spectral sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but as described above, it may be dispersed in any step of preparation in the silver halide emulsion. Can be dispersed. In the present invention, the following compounds represented by (III) and (IV) described in JP-A-63-89838 may be used together with the above-mentioned sensitizing dye for the purpose of further enhancing the supersensitizing effect. it can.

[0066]

[Chemical 25]

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention in addition to the above, for example:
You can use the ones listed below. Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, lower column, 6 its manufacturing line to page 10, upper right column, 12th column, 3-245 37 Gazette, page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11 lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggant, JP-A-2-68539, page 10, lower left column, line 17 Stabilizers to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 6) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 plasticizer, from page 10 to upper right column, line 10, from page 14, lower left column, line 10 to lower right column, line 1

7) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 8) Film agent JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 9) Support, JP-A-2-68539, page 13, upper right column, line 7 to line 20. 10) Dyes / mordanting agents JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 11) Polyhydroxy JP-A-3-39948, page 11, upper left column to the same benzene, page 12, lower left column, EP Patent No. 452772A. 12) Layer structure JP-A-3-198041. 13) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10

[0069]

【Example】

Example 1 1. Preparation of silver halide emulsion 34 g of gelatin was dissolved in 850 ml of H ₂ O, and 1.7 g of sodium chloride, 0.1 g of potassium bromide and the following compound (A) were placed in a container heated at 50 ° C.

[0070]

[Chemical formula 26]

After adding 70 mg of the above, 500 ml of an aqueous solution containing 170 g of silver nitrate was added to hexachloroiridium (I) so that the molar ratio of iridium to the finished silver halide was 2 × 10 ^-8.
II) An average particle size of 0.35 was obtained by adding 500 ml of an aqueous solution containing potassium acid, 18.1 g of sodium chloride and 85.7 g of potassium bromide by the double jet method.
Micron cubic monodisperse silver chlorobromide grains were prepared. After desalting this emulsion, 50 g of gelatin was added, and the pH was adjusted to 6.5.
After adding 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid to pAg 7.5 with aCl and chemically aging at 65 ° C., 4-hydroxy-6-methyl-1,3,3a,
0.1 g of 7-tetrazaindene was added and rapidly solidified (emulsion c).

Then, the same procedure as described above was carried out except that the iridium compound was not added to the above-mentioned sodium chloride / potassium bromide halogen-added solution (emulsion e). Then emulsion c
Then, an emulsion f was prepared in exactly the same manner except that the amount of gelatin added after the desalting treatment was 64 g. Next, an emulsion d was prepared in exactly the same manner except that the gelatin addition after the desalting treatment with the emulsion c was 41 g. Next, in emulsion c, add 3 parts each of sodium chloride and sodium bromide in the halogenated solution.
Emulsion a was prepared in exactly the same manner except that the amounts were 6.1 g and 49.0 g. Next, in emulsion c, 3.0 g of sodium chloride and sodium bromide of the halogen-containing solution were added, respectively.
Emulsion b was prepared in exactly the same manner except that the amount was 6.3 g.

2. Preparation of emulsion coating solution For each of emulsions a), b), c), d), e), c), and f), the following additives were added per mol of silver halide in the emulsion: emulsion coating solution i), ii) , Iii), iv), v), viii)
, Ix).

A) Spectral sensitizing dye A1 2 × 10 ^-5 mol) Supersensitizer III 3 × 10 ^-4 mol c) Preservation improver IV 1 × 10 ^-4 mol d) Polyacrylamide (molecular weight 4 10,000) 7.5 g E) Dextran 7.5 g F) Trimethylolpropane 1.6 g To) Na polystyrene sulfonate 1.2 g Thi) Poly (ethyl acrylate / methacrylic acid) latex 12 g Re) N, N'-ethylenebis -(Vinyl sulfone acetamide) 3.0 g

Using emulsion c as the sensitizing dye A101,
Otherwise, use the same coating solution as above for emulsion coating solution vi.
i). The emulsion coating solution vi) was the same as the above coating solution except that the sensitizing dye was changed to A2 by using the emulsion c.

[0076]

[Chemical 27]

3. Preparation of Emulsion Layer Surface Protective Layer Coating Solution A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Formulation of coating solution for emulsion layer surface protection layer)

B. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. The amount was adjusted to 1.4 wt% with respect to the amount of N, N'-ethylenebis- (total zelanacetamidoamido of vinylsulfone emulsion layer and protective layer) tin. E. Polymethylmethacrylate fine particles (average particle size 2.0 μm) 2.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Ji. Sodium polyacrylate 6.0 g Re. C ₈ F ₁₇ SO ₃ K 70 mg Nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 70 mg ru. 6 ml of NaOH (1N). Methanol 90 ml Wa. Compound [5] 0.06 g

[0079]

[Chemical 28]

4. Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the formulation shown below to prepare a back layer coating liquid.

(Back Layer Coating Liquid Formulation-1) a. Gelatin 100 g b. Dye [25] 4.2 g c. Polystyrene sodium sulfonate 1.2 g d. Poly (ethyl acrylate / methacrylic acid latex) 5 g E.N, N'-ethylenebis- (vinylsulfoneacetamide) 4.8 g F. Compound [5] 0.06 g G. Dye [C] 0.3 g D. D ] 0.05 g Li. Colloidal silica 15 g

[0082]

[Chemical 29]

(Back layer coating formulation-2) The dye [25] of the back layer coating formulation-1 was changed to the dye [101].

[0084]

[Chemical 30]

5. Preparation of Back Surface Protective Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating liquid.

(Prescription of coating solution for back surface protective layer)

B. Gelatin 100 g b. Polystyrene sodium sulfonate 0.5 g c. N, N′-ethylenebis- (total zenacetamido of vinylsulfoback layer and protective layer) It was adjusted to be 2.2 wt% with respect to the amount of latin. D. Polymethylmethacrylate fine particles (average particle size 4.0 μm) 4 g e. Sodium t-octylphenoxyethoxyethane sulfonate 2.0 g f. NaOH (1N) 6 ml. Sodium polyacrylate 2.4 g h. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Li. C ₈ F ₁₇ SO ₃ K 70 mg Nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 70 mg. Methanol 150 ml Wa. Compound [5] 0.06 g

6. Creating photographic material

The above coating solution for the back layer, together with the coating solution for the surface protective layer of the back layer, was applied to one side of the polyethylene terephthalate support at a gelatin coating amount of the back of 2.0 g / m ² ,
The back surface protective layer was coated such that the coating amount of gelatin was 1.0 g / m ² and the total coating amount of gelatin was 3 g / m ² . Subsequently, the emulsion coating liquid and the surface protective layer coating liquid were coated on the opposite side of the support in a combination according to the purpose.

Table 1 summarizes the contents of the coating layers 1 to 9 on the emulsion layer side and the back layer side.

[0091]

[Table 1]

7. (Evaluation of Samples) The coated samples 1 to 9 were kept at 25 ° C. and a temperature and humidity of 60% RH for 7 days and then subjected to various evaluations. 1) Exposure and processing The exposure is the laser imager F manufactured by FUJIFILM Corporation.
830 The semiconductor laser part of L-IM3543II is remodeled.
nm and 810 nm were used for scanning exposure for 10 ⁻⁷ seconds. There were three types of processing, Dry to Dry 90 ″, 45 ″ and 30 ″. 90 ″ is an automatic developing machine FPM-5000, a developing solution RD-3, a fixing solution Fuji F, manufactured by FUJIFILM Corporation.
35 ° standard 90 seconds. 45 ″ is an automatic developing machine CEPROS-M, a developing solution CED manufactured by FUJIFILM Corporation
-1, fixing solution CEF-1, 35 ° standard 45 seconds. For 30 ", the drive shaft of CEPROS-M was modified to increase the drive speed to Dry to Dry 30 seconds, and the developing solution and the fixing solution were 35 ° 30 seconds as described below.

Developer (I) PartA potassium hydroxide 18.0 g potassium sulfite 75.0 g sodium carbonate 30.0 g boric acid 5.0 g diethylene glycol 10.0 g diethylenetriaminepentaacetic acid 2.0 g 1- (N, N diethylamino) ethyl- 5-Mercaptotetrazole 0.1 g Hydroquinone 27.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.0 g Water was added to 300 ml.

Part B Triethylene glycol 45.0 g 3,3′-dithiobishydrocinnamic acid 0.2 g Glacial acetic acid 5.0 g 5 Nitroindazole 0.3 g 1-Phenyl-3-pyrazolidone 3.5 g Water 60 ml

PartC Glutaraldehyde (50%) 10.0 g Potassium bromide 1.0 g Potassium metabisulfite 10.0 g Water was added to 50 ml PartA 300 ml, PartB 60 ml and PartC5
Add water to 0 ml to make 1 liter and adjust to pH 10.50.

Fixer (I) Ammonium thiosulfate (70 wt / vol%) 200 ml Ethylenediaminetetraacetic acid disodium dihydrate 0.03 g Sodium sulfite 15.0 g Boric acid 4.0 g 1- (N, N-dimethylamino)- Ethyl-5-mercaptotetrazole 1.0 g Tartaric acid 3.0 g Sodium hydroxide 15.0 g Sulfuric acid (36N) 3.9 g Aluminum sulfate 10.0 g Water was added to 1 liter (adjusted to pH 4.60).

The exposure, treatment, and test items carried out for each sample and the results thereof are summarized in Table 2.

[0098]

[Table 2]

2) Evaluation of Sensitivity a) Sensitivity with 830 nm laser exposure: 830 nm semiconductor laser scanning exposure was used to perform wedge exposure for sensitometry, and the density was measured with a Macbeth densitometer to obtain a characteristic curve. CEPROS-M treatment for 30 seconds, the relative sensitivity of Sample 3 was set to 100, and the sensitivity of the combination of other samples and treatment was displayed as a relative value. B) Sensitivity at 810 nm exposure: The same as 2) -a) above except for 810 nm semiconductor laser scan exposure. A relative sensitivity of 80-140 was within the controllability of the laser imager and was considered acceptable.

3) Gradation evaluation On the characteristic curve obtained in 2) above, the gradient of the straight line connecting the two points of fog +0.25 and fog +2.0 is taken as the gradation G
_Shown at _0.25-2.0 . Gradations of 2.0 to 3.5 are within the controllability of the laser imager, and are considered to be acceptable.

4) Evaluation of Dmin The optical density of the unexposed portion of the characteristic curve obtained in 2) above was taken. If there is residual infrared dye on the back, it will be colored blue and unsuitable for diagnosis. D = 0.22 or less No inconvenience in diagnosis ○ 0.22 or more Inconvenience in diagnosis, out of tolerance × 0.3 or more Inferior in diagnosis, not suitable at all

5) Evaluation of Drying Property A half-cut film was processed every 10 seconds with each automatic developing machine set under standard conditions in a bright room at room temperature and humidity, and the processed film after passing 50 sheets was processed. It was judged according to the following criteria. I feel no tightness when I touch it ◎ I do not feel tightness when I touch it ○ I feel tightness when I touch it. Unacceptable × 6) Evaluation of silver tone A chest image was laser-printed, processed by each automatic developing machine set under standard conditions, and observed on a Schaukasten. Diagnosis becomes difficult when the silver tone is closer to the brown side. The following criteria were used according to the degree of that. Black tone that is not inconvenient for image reading ○ Warm black tone that is difficult to read

7) Evaluation of Sharpness A rectangular wave pattern for CTF measurement was laser-printed to a uniform density of D≈0.8 and D≈1.5, and each automatic developing machine set under standard conditions. Was measured, the micro-concentration was measured, and the CTF curve was obtained. It was judged according to the following criteria. CTF 0.9 or more at 5 lines / mm ◎ 0.7 or more ○ 0.5 or less Not permissible × (clearly bleeding)

8) Evaluation of Fixability The unexposed half-cut sample was processed by each automatic developing machine set under standard conditions, and the degree of remaining silver halide emulsion grains remaining due to poor fixing was visually observed. It was observed and judged according to the following criteria. No residue at all ◎ No residue at all ○ Light island-like residue slightly present, not acceptable ×

9) Comprehensive Evaluation Any one of the seven test items having an unacceptable x was judged to be unsuitable by the comprehensive judgment.

8. The results are summarized in Table 2. Only the present invention is suitable for comprehensive judgment.

Example 2 1. Preparation of silver halide emulsion 1. Among the preparation methods of emulsion c described in the section of preparation of silver halide emulsion, the heating temperature of the container was changed to 55 ° C., the iridium / silver molar ratio was changed to 1.1 × 10 ^−8, and the chemical ripening was performed. The amount of sodium thiosulfate for use was changed to 2.0 mg, and 3 mg of sodium benzenethiosulfonate was further added for ripening to prepare a cubic g monodisperse emulsion g having an average grain size of 0.43 μm. The heating temperature of the emulsion container was changed to 40 ° C., and the iridium / silver molar ratio was 2.2 × 10.
^-8 , the sodium thiosulfate for chemical ripening was changed to 3.5 mg, and the cube had a mean particle size of 0.
A 29 μ monodisperse emulsion h was prepared.

2. Preparation of emulsion coating solution The emulsion of the emulsion coating solution i) described in the section of the preparation of the emulsion coating solution was changed to a mixture of the emulsion g and the emulsion h in an equal amount, and c) a storage stability improver IV 1 × 10 ⁻⁴ mol / mol Ag
Was changed to 2 × 10 ⁻⁴ mol / mol Ag for the storage stability improvers [5] and [6] to prepare an emulsion coating solution xi).

[0109]

[Chemical 31]

The emulsion coating solution xii) was prepared by changing the spectral sensitizing dye A1 of the emulsion coating solution xi) to the spectral sensitizing dye A101.

3. Preparation of emulsion layer surface protection layer coating solution The same solution as in Example 1 was used.

4. Preparation of Back Layer Coating Liquids Back layer coating liquids 1 and 2 according to the back layer coating liquid formulations -1 and -2 of Example 1 were used.

5. Preparation of Back Layer Surface Protective Layer Coating Solution The same back layer surface protective layer coating solution of Example 1 was used.

6. Creating photographic material

The above back layer coating solution, together with the back layer and surface protective layer coating solution, was applied to one side of the polyethylene terephthalate support at a gelatin coating amount of 2.3 g / m ² of the back.
The back surface protective layer was coated such that the coating amount of gelatin was 1.0 g / m ² and the total coating amount of gelatin was 3.3 g / m ² . Subsequently, the emulsion coating solution and the surface protective layer coating solution were combined and coated on the opposite side of the support according to the purpose.

The contents on the emulsion layer side and the back layer side of the coated samples 11, 12, and 13 are summarized in Table 3.

[0117]

[Table 3]

7. Evaluation of Samples The coated samples 11, 12 and 13 were kept at 25 ° C. and 60% RH temperature and humidity for 7 days and then subjected to various evaluations.

1) Exposure and Treatment The exposure was the same as the exposure described in Example 7-1).
For processing, the drive shaft of the automatic developing machine CEPROS-M manufactured by FUJIFILM Corporation was modified so that the dry to dry time was 30 seconds, and the drive speed was increased. Developer (I) and fixer (I) described in 1)
Was used.

The exposure, processing, and test items carried out for each sample and the results thereof are summarized in Table 4.

[0121]

[Table 4]

2) Evaluation of sensitivity a) Sensitivity at 830 nm laser exposure: 830 nm semiconductor laser scanning exposure, sensitometric exposure, CEPROS-M treatment for 30 seconds, density measurement by Macbeth densitometer to obtain characteristic curve It was Relative sensitivity of sample 11 is 1
As 00, the sensitivities of the other samples are displayed in relative terms. B) Sensitivity with 810 nm laser exposure: Same as 2) -a) above except for 810 nm semiconductor laser scan exposure. A relative sensitivity of 80-140 was within the controllability of the laser imager and was considered acceptable.

3) Gradation evaluation On the characteristic curve obtained in 2) above, the gradient of the straight line connecting the two points of fog +0.25 and fog +2.0 is taken as the gradation G
_Shown at _0.25-2.0 . Gradations of 2.0 to 3.5 are within the controllability of the laser imager, and are considered to be acceptable. 4) Evaluation of Dmin: Evaluation of drying property, evaluation of silver tone, evaluation of sharpness, evaluation of fixing property, and comprehensive judgment were performed in the same manner as in Example 1.

8. The results are summarized in Table 4. Only the present invention is suitable for comprehensive judgment.

[Procedure amendment]

[Submission date] October 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

Grain formation is preferably cubic, but tabular grains having a spherical shape, a potato shape, a plate shape, and an aspect ratio of 5 or more as long as they satisfy the surface index conditions of the present invention (for details, see Research Disclosure Item No. 22534
P. 20-p. 58)) and an irregular crystal form. These light-sensitive silver halide emulsions may be mixed with a substantially non-light-sensitive silver halide emulsion (eg, internally fogged fine grain emulsion). Of course, emulsions having different grain sizes, halogen compositions, etc. may be separately coated in different layers to increase the exposure latitude. A narrow so-called monodisperse particle size distribution is preferably used. More specifically, as a monodisperse emulsion, 90% or more of all grains within ± 40% of the average grain size, preferably 9% of all grains within ± 20%.
An emulsion containing 0% or more is preferable. Furthermore, even if the crystal structure of the silver halide grains is uniform to the inside,
Also, a layered structure in which the inside and the outside are different, British Patent No. 635,841 and US Patent No. 3,622,318.
As described above, it may be a so-called conversion type, or may be a type in which a latent image is mainly formed on the surface or an internal latent image type in which the latent image is formed inside the grain.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction content]

[0066]

[Chemical 25]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

After adding 70 mg of the above, 500 ml of an aqueous solution containing 170 g of silver nitrate and hexachloroiridium (I) so that the molar ratio of iridium and finished silver halide is 2 × 10 ^-7.
II) An average particle size of 0.35 was obtained by adding 500 ml of an aqueous solution containing potassium acid, 18.1 g of sodium chloride and 85.7 g of potassium bromide by the double jet method.
Micron cubic monodisperse silver chlorobromide grains were prepared. After desalting this emulsion, 50 g of gelatin was added, and the pH was adjusted to 6.5.
After adding 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid to pAg 7.5 with aCl and chemically aging at 65 ° C., 4-hydroxy-6-methyl-1,3,3a,
0.1 g of 7-tetrazaindene was added and rapidly solidified (emulsion c).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

[0079]

[Chemical 28]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction content]

7. (Evaluation of Samples) The coated samples 1 to 9 were kept at 25 ° C. and a temperature and humidity of 60% RH for 7 days and then subjected to various evaluations. 1) Exposure and processing The exposure was carried out by modifying the semiconductor laser section of the laser imager FL-IM3543II manufactured by Fuji Photo Film Co., Ltd. 8
Scanning exposure was performed at 30 nm and 810 nm for 10 ⁻⁷ seconds. Treatment is Dry to Dry 90 ″, 45 ″, 30 ″ 3
It was a kind. 90 "is Fuji Photo Film Co., Ltd., automatic processor FPM-5000, developer RD-3, fixer Fuji F, 35 ° standard 90 seconds. 45" is Fuji Photo Film Co., Ltd. Automatic developing machine CEPROS-M, developing solution CED-1, fixing solution CEF-1, 35 ° standard 45 seconds. For 30 ″, the drive shaft of CEPROS-M was modified to increase the drive speed to Dry to Dry 30 seconds, and the developer and fixer were 35 ° dry to dry as follows.
It was set to 30 seconds.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0102

[Correction method] Change

[Correction content]

5) Evaluation of Drying Property A half-cut size film was processed every 10 seconds with each automatic developing machine set under standard conditions in a bright room at room temperature and humidity, and the processed film after passing 50 sheets was as follows. It was judged according to the standard. I feel no tightness when I touch it ◎ I do not feel tightness when I touch it ○ I feel tightness when I touch it. Unacceptable × 6) Evaluation of silver tone A chest image was laser-printed, processed by each automatic developing machine set under standard conditions, and observed on a Schaukasten. Diagnosis becomes difficult when the silver tone is closer to the brown side. The following criteria were used according to the degree of that. Black tone that is not inconvenient for image reading ○ Warm black tone that is difficult to read

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0104

[Correction method] Change

[Correction content]

8) Evaluation of Fixing Property An unexposed half-size sample was processed by each automatic developing machine set under standard conditions, and the degree of residual silver halide emulsion grains remaining due to poor fixing was visually observed. It was judged according to the following criteria. No residue at all ◎ No residue at all ○ Light island-like residue slightly present, not acceptable ×

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

10) The results are summarized in Table 2. Only the present invention is suitable for comprehensive judgment.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0107

[Correction method] Change

[Correction content]

Example 2 1. Preparation of silver halide emulsion 1. Among the preparation methods of emulsion c described in the section of preparation of silver halide emulsion, the heating temperature of the container was changed to 55 ° C., the iridium / silver molar ratio was changed to 1.1 × 10 ^−7, and the chemical ripening was performed. The amount of sodium thiosulfate for use was changed to 2.0 mg, and 3 mg of sodium benzenethiosulfonate was further added for ripening to prepare a cubic g monodisperse emulsion g having an average grain size of 0.43 μm. The heating temperature of the emulsion container was changed to 40 ° C., and the iridium / silver molar ratio was 2.2 × 10.
^-7 , the sodium thiosulfate for chemical ripening was changed to 3.5 mg, and it was cubic and had an average particle size of 0.
A 29 μ monodisperse emulsion h was prepared.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0108

[Correction method] Change

[Correction content]

2. Preparation of emulsion coating solution The emulsion of the emulsion coating solution i) described in the section of the preparation of the emulsion coating solution was changed to a mixture of the emulsion g and the emulsion h in an equal amount, and c) a storage stability improver IV 1 × 10 ⁻⁴ mol / mol Ag
Was changed to 2 × 10 ⁻⁴ mol / mol Ag for each of the storage stability improvers [V] and [VI] to prepare an emulsion coating solution xi).

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0119

[Correction method] Change

[Correction content]

1) Exposure and Treatment The exposure was the same as the exposure described in Example 7-1).
The processing was carried out by modifying the drive shaft of the automatic developing machine CEPROS-M manufactured by Fuji Photo Film Co., Ltd. for 30 seconds to dry to dry, and increasing the drive speed. The developer (I) and the fixer (I) described in section -1) were used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03C 1/76 502 1/83

Claims (3)

[Claims] 1. A photosensitive halogen on one side of a transparent support.
It has a silver halide emulsion layer, and the silver halide emulsion has a coating silver amount of
2.8 g / m²Hereafter, all gelatin coating on the side with the emulsion layer
The amount is 3.5g / m²And the silver halide emulsion is
The spectral sensitizing dye represented by the general formula [I] is 810 to 840.
spectrally sensitized to the wavelength range of nm and the other side of the support
At least one of the hydrophilic colloid layers has the general formula [IIa],
Selected from compounds represented by [IIb] and [IIc]
It contains at least one dye and is dry to automatic
Dry Silver halide photosensitive material processed in 45 seconds or less. [Chemical 1][In the formula, Z_Five, Z₆Is a 5- or 6-membered nitrogen-containing heterocycle
Represents the atomic group necessary to form. Q_FiveIs 5, 6 or
Represents the atomic group necessary to form a 7-membered ring. R_Four, R
_FiveRepresents an alkyl group. L₃₂, L₃₃, L₃₄, L₃₅, L
₃₆, L₃₇, L₃₈, L₃₉, L₄₀Is a methine group or substituted meth
Represents a group. It may also form a ring with another methine group.
Or may form a ring with the auxochrome. n₈, N₉Is
Represents 0 or 1. M_FiveRepresents a charge neutralizing counterion
Then m_FiveIs 0 or more necessary to neutralize the charge in the molecule.
It is the number above. ] [Chemical 2]In the formula, Y¹And Y²Are each a chalcogen atom, -CH =
CH- group, -N (R^Ten) -Group (R^TenRepresents an alkyl group
), Or -C (R^Ten) (R¹¹) -Group (R^TenAnd R¹¹Is
Each represents an alkyl group), Z¹And Z²Is benzo
Non-metallic source necessary to form fused or naphtho fused rings
Represents a group of children. R¹And R²Each represents an alkyl group,
L may be the same or different and each represents a methine group,
At least one of L is -OR¹²Group (R¹²Is an acidic substituent
A substituted alkyl group or aryl group),-
N (R¹²) (R¹³) Group (R¹²Is as defined above, R¹³Is hydrogen
An alkyl group, substituted with an atom or an acidic substituent, or
Represents an aryl group), -SR ¹²Group (R¹²Is synonymous with the above)
Or -CH (R¹⁴) (R¹⁵) Group (R¹⁴And R¹⁵Are each
Cyano group, carboxylic acid group, acyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
Represents a group, a sulfonyl group or a sulfamoyl group. However
And R¹⁴Or R¹⁵At least one of them contains an acidic substituent.
Let's assume. ) Represents a methine group substituted with
Represents a nonion, p is 0 or 1, r is 0 or 1,
m represents 2 or 3, and n represents 1 or 2. Dye is a molecule
N is 1 when forming an inner salt. However, in the dye molecule
Have at least 3 acidic substituents. [Chemical 3]Where Z¹And Z²Is a benzo-condensed ring or a naphtho-condensed ring
Represents a group of non-metal atoms necessary for forming. R¹,
R², R³, R^Four, R^FiveAnd R⁶Each represents an alkyl group
And L may be the same or different and each represents a methine group.
And at least one of L is -OR¹²Group (R¹²Is acidic substitution
Represents an alkyl group or an aryl group substituted with a group,
Here, it also means a "substituted aryl group"),-
N (R¹²) (R¹³) Group (R¹²Is as defined above, R¹³Is hydrogen
An alkyl group, substituted with an atom or an acidic substituent, or
Represents an aryl group), -SR¹²Group (R¹²Is synonymous with the above)
Or -CH (R¹⁴) (R¹⁵) Group (R¹⁴And R¹⁵Are each
Cyano group, carboxylic acid group, acyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
Represents a group, a sulfonyl group or a sulfamoyl group. However
And R¹⁴Or R¹⁵At least one of them contains an acidic substituent.
Let's assume. ) Represents a methine group substituted with
Represents nion, m represents 2 or 3, and n represents 1 or 2.
You N is 1 when the dye forms an inner salt. However
However, the dye molecule contains at least four acidic substituents.
And [Chemical 4]Where Z¹And Z²Is a benzo-condensed ring or a naphtho-condensed ring
Represents a group of non-metal atoms necessary for forming. R¹,
R², R³, R^Four, R^FiveAnd R⁶Are each an alkyl group
Represent, R⁷And R⁸Is a hydrogen atom or both 5 or 6 members
Represents a group of non-metal atoms necessary for forming a ring, R⁸Is -O
R¹²Group (R¹²Is an alkyl group substituted with an acidic substituent or
Represents an aryl group), -N (R¹²) (R¹³) Group (R¹²
Is as defined above, R¹³Is a hydrogen atom or an acidic substituent
Represents an alkyl group or an aryl group), -SR
¹²Group (R¹²Is as defined above) or -CH (R¹⁴)
(R¹⁵) Group (R¹⁴And R¹⁵Are cyano group and carboxylic acid, respectively
Group, acyl group, alkoxycarbonyl group, aryloxy
Sicarbonyl group, carbamoyl group, sulfonyl group or
Represents a sulfamoyl group. However, R¹⁴Or R¹⁵Little
At least one shall contain an acidic substituent), and X
Represents an anion, and n represents 1 or 2. Dye is a molecule
N is 1 when forming an inner salt. However, within the dye molecule
Include at least 4 acidic substituents. 2. The silver chloride content of the silver halide emulsion is 1
The silver halide light-sensitive material according to claim 1, which is 0 mol% or more and 50 mol% or less. 3. The silver halide light-sensitive material according to claim 1, wherein the silver halide emulsion has an iridium compound content of 5 × 10 ⁻⁸ mol / mol Ag or more.