JPH0486739A - Silver halide photographic sensitive material spectrally sensitized in infrared region - Google Patents

Abstract

PURPOSE:To improve storage stability and to prevent color stains due to residual dyes by incorporating an emulsion containing a spectrally sensitizing dye and iondine ions in a photosensitive silver halide emulsion layer spectrally sensitized in a specified wavelength region. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers spectrally sensitized in the wavelength region of >= 750 nm contains the solution of the spectrally sensitizing dye and the iodine ions, and the infrared sensitizing dye, for example, preferably, represented by formula I in which each of Z<1> and Z<2> is a nonmetallic atomic group necessary to form a benzothiazole ring; each of R<1> and R<2> is a saturated or unsaturated aliphatic group; Z<2> is a 5- or 6-membered carbon ring; A is H when Z<2> is a 6-membered ring. The compound for releasing iodine ions to be used is, such as sodium, potassium or ammonium iodide, thus permitting storage stability under high temperature and high humidity to be improved and color stains due to residual dyes to be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material spectrally sensitized to a wavelength range of 750 nm or more. A photosensitive material spectrally sensitized in the infrared region in this manner can be used, for example, as a photosensitive material for a laser light source.

[Background of the invention]

In recent years, attempts have been made to capture, for example, radiographic images for medical diagnosis as digital values, perform image processing using a computer to make them more suitable for diagnosis, and then expose the image to a laser beam to reproduce the image.

As lasers for these scanning exposure apparatuses, argon, helium-neon, helium-cadmium and other lasers have been put into practical use. However, all of these lasers have drawbacks such as short lifespan, large size, and the need for complicated equipment to modulate the emission intensity.

In response, research into semiconductor lasers has recently progressed, resulting in increased power and longer lifespans.

Semiconductor lasers have advantages over conventional argon and helium-neon lasers, such as being cheaper and longer lasting, smaller in size, and capable of direct modulation, eliminating the need for a modulator.

However, since the emission wavelength of the semiconductor laser having the above-mentioned characteristics is in the near-infrared region of 750 to 1,500 nm, the recording material must also have a photosensitive region in the near-infrared region.

As a method for spectrally sensitizing silver halide to near-infrared light,
For example, The Theory of the Photographic
The Theory of the Pho
tographic Process) 3rd edition, published by Macmillan (1966), 19
As shown on pages 8 to 201, methods using long-chain cyanine dyes are known.

[Problem that the invention seeks to solve]

However, these conventional photosensitive materials have the disadvantage of very poor storage stability. In order to overcome this drawback, the present applicant discovered a technique of adding water-soluble iodide to the silver halide emulsion before adsorbing the spectral sensitizing dye (Japanese Patent Application Laid-open No. 1-288850), and this technique has achieved a certain degree of success. Although it is thought to have produced results, the storage stability under high temperature and high humidity conditions was still insufficient.

Furthermore, the development processing time of photosensitive materials is becoming shorter (ultra-rapid processing), but in the conventional photosensitive materials mentioned above, dyes remain when rapid processing is performed.
There is a so-called problem of residual color.

The present invention solves these problems and is spectrally sensitized to a wavelength range of 750 nm or more, has good storage stability, especially under high temperature and high humidity, and can be processed quickly. It is an object of the present invention to provide a silver halide photographic material that does not cause color residue even when exposed to light.

[Means for solving problems]

As a result of various studies, the present inventor has found that the above object is to have at least 1N of a photosensitive silver halide emulsion layer that is spectrally sensitized to a wavelength range of 750 nm or more, and to provide at least one of the photosensitive silver halide emulsion layers. It has been discovered that the layer can be achieved by a silver halide photographic light-sensitive material characterized by containing a milkyel added with a solution in which a spectral sensitizing dye and an iodide ion are dissolved, and the present invention has been achieved. completed.

The photosensitive material of the present invention can be used, for example, as a photosensitive material for laser scanners.

The present invention will be explained in more detail below.

In the light-sensitive material of the present invention, at least one silver halide emulsion layer is spectrally sensitized to a wavelength range of 750 nm or more.

As a means for spectral sensitization to such a wavelength range, a method using a spectral sensitizing dye can be used.

In the present invention, for such spectral sensitization, it is preferable to perform spectral sensitization using the following infrared sensitizing dye. That is, it is preferable to perform spectral sensitization with at least one compound selected from the group consisting of the compound represented by the following general formula [I] and the compound represented by the general formula (II).

General formula (N Z2 represents a 5- or 6-membered carbon atom ring, A represents a hydrogen atom when Z2 is a 6-membered ring. When 22 is a 5-membered ring,
General formula CI] is preferably represented by the following general formula [Ia].

General formula CI-a) In the formula, z' and z' are a benzothiazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, which may have a substituent,
It represents a group of nonmetallic atoms necessary to form a naphthoxazole nucleus, and R1 and RZ each represent a saturated or unsaturated aliphatic group.

vinegar.

R3 and R' each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms, and R' and R6 each represent an alkyl group having 1 to 12 carbon atoms, alkoxycarbonyl Represents an alkyl group or an allyl group that may have a substituent, and R7 has 1 to 1 carbon atoms.
2 alkyl group, an allyl group having 6 to 10 carbon atoms, or an alkoxycarbonyl group having 1 to 4 carbon atoms.

When Z2 is a 6-membered ring, the general 2CIE is the following general formula (1-
It is preferable that it is represented by b).

General formula [1-b) 8 R9 \, / In the formula, RI' represents a hydrogen atom or a methyl group, and R9 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monocyclic aryl group. X61 represents an anion, n is 1 or 2 (
When forming an inner salt, n is 1).

A further explanation of the infrared sensitizing dye represented by the general formula [■] that can be preferably used in the present invention is as follows.

In the general formula [l), ZI and Zff represent a group of nonmetallic atoms necessary to form a benzothiazole nucleus, benzoxazole nucleus, naphthothiazole nucleus, or naphthoxazole nucleus that may have a substituent, and as a substituent, Examples include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

R' and R2 each represent a saturated or unsaturated aliphatic group (e.g. methyl group, ethyl group, 2-hydroxyethyl group, 2-
Methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4
-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, p-sulfophenethyl group, n-propyl group,
isopropyl group, n-butyl group, etc.).

Z2 represents a 5- to 6-membered carbon atom ring, and when Z2 is 6-membered, A represents a hydrogen atom. In the case of a 5-membered ring, the general formula (
Those represented by 1-a) are preferred.

General formula CI-a], R'' and R' are each a hydrogen atom,
Alkyl group having 1 to 4 carbon atoms, halogen atom, 1 to 4 carbon atoms
4 alkoxy group, R5R6 each has 1 carbon number
~12 alkyl groups, alkoxycarbonylalkyl groups (e.g., methoxycarbonylmethyl group, ethoxycarbonylethyl group, etc.), allyl groups that may have substituents (e.g., phenyl group, m-tolyl group, p-tolyl group, m-chlorophenyl group, P-chlorophenyl 4, carbon number 1-4
R7 represents an alkyl group having 1 to 12 carbon atoms, an allyl group having 6 to 10 carbon atoms, or an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms. represents a group.

When Z2 is 6-membered, those represented by the general formula C1b) are preferred.

General formula [1-N, R8 is a hydrogen atom or a methyl group, R
9 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monocyclic aryl group.

) (e represents an anion. For example, chloride ion, bromide ion, iodide ion, perchloric acid, Hensensulfonate, P
Represents -1-luenesulfonate, methyl sulfate, ethyl sulfate, tetrafluoroboric acid, etc.

n represents 1 or 2 (n is 1 when forming an inner salt).

Next, typical examples of the compound represented by the general formula [I] will be given. However, it goes without saying that the invention is not limited to the examples below.

Margin below ■ 1; hH5 6115 ! -6 ■ ■-13 C) 12COOH 2H5 ■ ■ ■ ■ ■ ■-17 ■-18 ■ ■ ■ ■ bns ■ ■ ■ ■-32 ■-33 ■ shizlls Shi2H5 ■-29 ■ zHs zHs ■ ■ Also, In the present invention, 750n sho In the wavelength range above To spectral sensitize, The following general formula (II) represented by 4 keno Uses non-nuclear dicarbocyanine dye It is also preferable to be there.

In the general formula ([[) General formula CII], R16 and R17 may be the same or different from each other, and each represents an alkyl group (including one having a substituent). The alkyl group preferably has 1 to 8 carbon atoms, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, and the like. As substituted alkyl groups,
The number of carbon atoms in the alkyl moiety is preferably 6 or less, and examples of the substituent include a carboxy group, a sulfo group, a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxy group, and an alkoxycarbonyl group. Group (
8 or less carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group)
, an alkoxy group (having 7 or less carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a benzyloxy group, etc.), an aryoxy group (such as a phenoxy group, an Il+-tolyloxy group, etc.), an acyloxy group ( Acyl groups (having 8 or less carbon atoms, such as acetyl, propionyl, hendiyl, mesyl, etc.), carbamoyl groups (such as carbamoyl, N,
N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarhamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (
Examples include phenyl group, p-hydroxyphenyl group, P-carboxyphenyl group, P-sulfophenyl group, α-naphthyl group, etc.).

Two or more of these substituents may be substituted into an alkyl group in combination.

R''1 represents a hydrogen atom, a lower alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), a lower alkoke group (e.g., metquine group, etquine group, propoxy group, butoxy group'4), phenyl group, hensyl group. represents.However, this R+
Preferably, a is a lower alkyl group or a Hensyl group.

■ is a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, butquine group, etc.), a halogen atom (e.g. fluorine atom, chlorine atom, etc.), or a substituted Represents an alkyl group (eg trifluoromethyl group, carboxymethyl group, etc.).

2+2 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. For example, thiazole nuclei (e.g. evabenzothiazole, 4-chlorhendithiazole, 5
-Chlorhendithiazole, 6-chlorhendithiazole, 7-chlorhendithiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodo Henzuthiazole,
5-phenylbenzothiazole, 5-methoquinohendithiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carpoquinhenzothiazole, 5-ethoxyluponylhenzothiazole, 5-phenethylbenzothiazole, 5- Fluorohendithiazole, 5-trifluoromethylbenzothiazole, 56-
dimethylhenzothiazole, 5-hydroxy-6methylbenzothiazole, tetrahydrohendithiazole, 4
-Phenylbenzothiazole, naphtho(2,1-d)thiazole, naphtho(1,2-d]thiazole, naphthoC
2,3-d) Thiazole, 5-methoxynaphtho[:1.
2-d) Thiazole, 7-nitoxynaphthoC2,1-d
) thiazole, 8-methoxynaphtho(2,1-d)thiazole, 5-methoxynaphtho(C2,3-d)thiazole, etc.), selenazole core (e.g. benzoselenazole, 5
-Chlorbenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho(2,1-d)selenazole, naphtho[1nzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-
Promhenzoxazole, 5-fluorohendioxazole, 5-phenylhendioxazole, 5-methoxyhenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlor Benzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 4,6-dimethylhenzoxazole, 5-ethoxybenzoxazole, naphtho(2,1-d:l oxazole, naphtho r1.2-a]oxazole, Naft C
2,3-d)oxazole etc.), quinoline nucleus (e.g. 2
-quinoline, 3-methyl-2-quinoline, 5-ethyl-
2-quinoline, 6-methyl 2-quinoline, 8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline,
8-fluoro-4-quinoline, etc.), 3.3-dialkylindolenine nuclei (e.g., 3,3-dimethylindolenine, 3.3-diethylindolenine, 33-dimethyl-
5-cyanoindolenine, 3.3-dimethyl-5-methoxyindolenine, 3.3-dimethyl-5-methylindolenine, 3.3dimethyl-5-chlorindolenine, etc.), imidazole nuclei (e.g. 1- Methylhenzimidazole, ■=Ethylbenzimidazole, ■-Methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5°6-dichlorobenzimidazole, 1-ethyl5. 6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-
Methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5
, 6-dichlorobenzimidazole, 171J/Lz-
5,6-dichlorobenzimidazole, ■-aryl 5
-Chlorbenzimidazole, ■Phenylhenzimitasole, 1-Phenylhenzimidazole, ■-Methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethyl hencyimidazole, 1-ethylnaphtho[1,2d) imidanor, etc.), pyridine core (e.g. pyridine, 5-
methyl-2-pyridine, 3-methyl-4-pyridine, etc.)
The nonmetallic atomic groups necessary to complete the nitrogen-containing heterocycle can be mentioned. Among these nuclei, preferred are a thiazole nucleus and an oxazole nucleus, more preferably a penduthiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a hendioxazole nucleus.

X represents an acid anion.

m, n+, and I' each represent 1 or 2.

Next, typical specific examples represented by general formula (U) will be given.

However, it goes without saying that the invention is not limited to the examples below.

(■ l) (■ t,zNs e (■ (■ (■ (n-9)) (■ (■ (■ (■ (■ (■ (II-13) (■ 14)) Js ■e ([-15) (I[-18) (n-19) (n-17) (It-20) (HzJ z3UxlNa In the present invention, the amount of the spectral sensitizing dye used is 0.003 g to 0.0 g per mole of silver halide. 3 g is preferred, and a range of 0.005 g to 0.15 g is particularly preferred.

Next, the present invention is a photographic material having an emulsion to which is added a spectral sensitizing dye for spectral sensitization to a wavelength range of 750 nm or more as described above, and a solution in which iodide ions are dissolved. Examples of the iodide ion compound used for this include sodium iodide, potassium iodide, and ammonium iodide. In addition, the amount of iodide used is
5.0X10-' to 1.0 per mole of halogenated il
Preferably it is X10-2 mol. Especially 1.0X1
A range of 0-' to 5.0 x 10-' moles is preferred.

Examples of the solvent used to dissolve the spectral sensitizing dye and iodide include water and organic solvents such as methyl alcohol, ethyl alcohol, acetone, fluorinated alcohol, and glycerol.

Alternatively, a mixed solution of water and those organic solvents may be used.

Next, silver halide emulsions that can be used to constitute the light-sensitive material of the present invention will be described.

The silver halide grains contained in the halogenated photographic material of the present invention are preferably silver halide containing silver iodide, and may be any of silver iodochloride, silver iodobromide, and silver chloroiodobromide. good. In particular, silver iodobromide is preferred from the standpoint of obtaining high sensitivity.

The average silver iodide content in such silver iodide-containing silver halide grains is preferably 0.5 to 10 mol%, more preferably 1 to 8 mol%, and the inside of the grain contains at least 20
There may be localized portions in which silver iodide is localized at a high concentration of mol % or more.

In this case, it is preferable that the localized portion inside the particle is located as far inward as possible from the outer surface of the particle, and it is particularly preferable that the localized portion exists in a portion that is 0.01 μm or more away from the outer surface.

Further, the localized portion may exist in a layered manner inside the particle, or may have a so-called core-shell structure, with the entire core serving as the localized portion. In this case, it is preferable that part or all of the core part of the grain excluding the shell part having a thickness of 0.01 μm or more from the outer surface is a localized part with a silver iodide concentration of 20 mol % or more.

Note that the concentration of silver iodide in the localized portion is preferably in the range of 30 to 40 mol%.

The outside of such localized areas is usually coated with silver halide without silver iodide. That is, in a preferred embodiment, the distance from the outer surface is 0.01 μm or more, particularly 0.01 μm or more.
A shell portion with a thickness of 0.01 to 1.5 μm is formed of silver halide (usually silver bromide) without silver iodide.

A method for forming a localized portion of high concentration silver iodide of at least 20 mol % inside the grain (preferably inside the grain at a distance of 0.01 μm or more from the outer wall of the grain) does not use seed crystals. There may be.

If seed crystals are not used, the reaction liquid phase containing the protected gelatin (
Since there is no silver halide to serve as growth nuclei in the mother liquor (hereinafter referred to as mother liquor) before the start of ripening, first, silver ions and halide ions containing high concentration iodide ions of at least 20 mol % are supplied to form growth nuclei. let Then, addition and supply are continued to grow particles from the growth nuclei. lastly,
A shell layer having a thickness of 0.01 μm or more is formed using silver halide containing no silver iodide.

If seed crystals are used, at least 20 mol% of the seed crystals alone
The above silver iodide may be formed and then covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is 0 or 10 mol%
Within the following range, at least 20 mol % of silver iodide may be formed inside the grains in the step of growing seed crystals, and then covered with a shell layer.

In the silver halide photographic light-sensitive material of the present invention, at least 50% of the silver halide grains present in the emulsion layer
is preferably a grain having a localized silver iodide portion as described above.

Another preferred embodiment of the present invention is to use a monodispersed emulsion having localized silver iodide portions as described above.

The monodisperse emulsion referred to herein means, for example, The
Photographic Journal, 79.
33 (1-338 (1939)) by Trivelli, S.
A silver halide emulsion in which at least 95% of the grains in terms of number or weight are within ±40%, preferably within ±30% of the mean grain diameter when the mean grain diameter is measured by the method reported by M1th. refers to something consisting of

Such monodisperse emulsion grains can be made using simultaneous mixing techniques, similar to ordered silver halide grains. The conditions for simultaneous mixing are the same as those for producing regular silver halide grains.

Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, , 12.242-251 (196
3) JP-A-48-36890, JP-A-52-16364, JP-A-55-142329, JP-A-58-4993
It is described in each publication No. 8.

In order to obtain the above-mentioned monodispersed emulsion, it is particularly preferable to use seed crystals and to supply silver ions and halide ions using the seed crystals as growth nuclei to grow grains.

The broader the particle size distribution of this seed crystal, the wider the particle size distribution of the particle growth nuclei. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use seed crystals with a narrow particle size distribution at the seed crystal stage.

The silver halide grains as described above used in the silver halide photographic light-sensitive material of the present invention are, for example, T, )l.

Written by James - The Theory of the
Photographic Process” 4th edition, M
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, Chondral-double jet method, conversion method, core/ It can be manufactured by applying a method such as a shell method.

The emulsion used in the silver halide photographic material of the present invention includes:
Known photographic additives can be used.

Examples of known photographic additives include Research Disclosure's RD-17643 and RD shown in the table below.
-18716.

Additives Chemical sensitizers Sensitizing dye development accelerators Antifoggants Stabilizers Ultraviolet absorbers Filters Dye hardeners Coating aids Surfactants Plasticizers Static inhibitors Matting agents Binder RD-17643 Page Classification 23 11 [ 23IV 29 XXI 24 Vl 24 ■ 25-26 ■ 25-26 ■ 26 X 26-27 XI 26-27 XI 27X [ 27XI 27X [ 28 − Upper right 649 - Lower right 649 - Lower right 649 Right - 650 Left 649 Right - 650 Left 651 Right 650 Right 650 Right 650 Right 650 Right 650 Left 651 left Reduction of so-called crossover effect in the silver halide photographic light-sensitive material of the present invention dyes can be used in layers below the emulsion layer in contact with the support, and dyes can also be added to the protective layer and/or emulsion layer to improve image sharpness or reduce fog caused by safe light. Dyes can be added.

As such a dye, any known dye for the above purpose can be used.

The perforated support used in the silver halide photographic light-sensitive material of the present invention includes all known ones, such as polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, styrene films, baryta paper, synthetic Paper coated with a polymer, etc. The emulsion of the present invention can be coated on one or both sides of the support, and when coated on both sides, the emulsion can be applied symmetrically or asymmetrically with respect to the support.

Although the present invention is applicable to all silver halide photographic materials, it is particularly suitable for high-sensitivity black-and-white or color negative photographic materials.

The silver halide photographic material of the present invention can be developed by a commonly used known method. The developer is
Commonly used developers, such as those containing hydroquinone, ■-phenyl-3-pyrazolidone, N-methyl-p-aminophenol, or p-phenylenediamine, alone or in combination of two or more thereof, are used; Commonly used additives can be used. Also,
When the photosensitive material is for color use, color development can be carried out by a commonly used color development method.

Developers containing aldehyde hardeners can also be used in the silver halide light-sensitive material of the present invention, such as dialdehydes such as mallei-thukudialdehyde, glutaraldehyde and their sodium bisulfite salts, etc. Developers known in the photographic field may also be used.

[Example] Hereinafter, the present invention will be further explained by examples.

However, it goes without saying that the present invention is not limited to this example.

Example-1 KB r 130g, KI 2.5g, 1-
Fi 500d containing 0.5 mol of ammoniacal silver nitrate in a stirred solution 11 containing 30 mg of phenyl-5-mer putotetrazole and 15 g of gelatin at 40°C.
was added over 1 minute, and 2 minutes after addition, acetic acid was added to bring the pH to 6.0. After a further 1 minute, 500ml of a solution containing 0.5 mol of silver nitrate was added over 1 minute, and after stirring for 15 minutes, an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to coagulate the emulsion.

After removing the supernatant liquid, add 2i of 40°C warm water, stir for 10 minutes, add an aqueous solution of magnesium sulfate again to coagulate the emulsion, and after removing the supernatant liquid, add 300 m of 5% gelatin/8 solution.
1 of the mixture was added and stirred at 55°C for 30 minutes to prepare an emulsion.

This emulsion has an average grain size of 0.40 μm and 0.20 μm.
90% of the total number of particles was contained in 0.70 μm.

The emulsion obtained above was kept at 55°C and chemically sensitized by adding ammonium thiosoanate, chloroauric acid and hypo, and then 4-hydroxy-6-methyl-1,3,3
a, 7-chitrazaindene was added to obtain a photosensitive emulsion.

All chemical ripening was carried out using ammonium thiocyanate 20.0 μm, chloroauric acid 5.0 μm, and hypo 15.0 μm per mole of silver halide. 4-hydroxy-6-methyl-1,3,3a was chemically aged at 52°C after each addition of Og and 100 minutes after the sensitizer was added.

7-Chitrazaindene was added.

In the present invention, an emulsion is used in which a solution in which a spectral sensitizing dye and iodide ions are dissolved is added. The amounts and positions of solution addition are shown in Table 1. Also, as a solvent for dissolving the spectral sensitizing dye and iodide, methanol:water - 1:1? A liquid solution was used.

On the other hand, a support was obtained in the following manner. i.e. gelatin 40
0 g, polymethyl methacrylate 2 g, sodium F-decylhenzenesulfonate 6 g, the following antihalation dye 20 g, and N,N'-ethylene bis-(vinylsulfonylacetamide), sodium polyethylene sulfonate. did. Glycidyl methacrylate 50-t%, methyl acrylate 10 wt%,
One side of a polyethylene terephthalate hese coated with an aqueous copolymer dispersion obtained by diluting a copolymer composed of three monomers containing 40 wt% butyl methacrylate to a concentration of 10-t% as an undercoat liquid. gelatin, capping agent (polymethyl methacrylate: average particle size 3.5 μm), glyoxal, sodium L-octylphenoxyethoxyethanesulfonate, and C, F, ? 502N(C3H7)CH2COOKCJ
I 73O□N (C3H?) (CH2CH20) +
The above-mentioned backing liquid was applied to the back side together with a protective layer liquid consisting of sH to prepare a backing support. The coating amount is 2.5g/r for the backing layer and the protective layer, each with gelatin coating amount.
d, 2.0 g/rrf.

(Antihalation dye) CH 1,1-dimethylollomethane 1-bromo-1-ditho10IIIg, Preparation of coating sample As an emulsion layer additive, per mole of silver halide, Trimethylolpropane Log, Nitrophenyl-triphenyl phosphonium chloride
50■, ammonium 1,3-dihydroxybenzene-4-sulfonate
1g, sodium 2-mercaptobenzimidazole-5-sulfonate
10 ml, etc. were added to form an emulsion layer, and an emulsion was prepared.

The protective layer liquid has the following composition. The amount added is shown in the amount per 12 coating liquids.

Lime-treated inert gelatin 68g Acid-treated gelatin 2gCH, C00
C. H21 (coating aid) Na0sS CHC00C
sHI+ g Polymethyl methacrylate, matting agent silicon dioxide particles with area average particle size of 3.5 μm matting agent with area average particles of 1.2 μm Ludox AM (manufactured by DuPont) (colloidal silica) 2-4-dichloro-6-hydroxy 1. 3.5-triazine sodium salt aqueous solution 2% (hardener) Formalin 35% (hardener) Glyoxal aqueous solution 40% (hardener) 1.1g 0.5g 0g 10-11.5d CHzCOO (CHz )9CH3 CHCOO(CH2) zcH(C)13) Zo, 3
g 03Na NaOzS CHC00CH2(C2F4):18C
HzCOOCHz (CzF4) J o, 5g F19C904CHzCHzO) rvcHzcHzOH
3■ C4F, 5OffK 2■ On the backed support, each layer was coated with the silver halide emulsion layer and the protective layer in order from the support using the slide homper method at a coating speed of 6.
A sample was obtained by applying two layers at a speed of 0 m/min. The amount of silver is 2.5 g/rf, the amount of gelatin is 3 g/r'rf in the emulsion layer,
The protective layer was 1.3 g/rrf.

The following evaluations were performed on the obtained samples.

(Measurement of sensitometry) After storing the obtained coated sample at 23°C and 155% RH for 3 days to stabilize the dura mater, the sample was stored for an additional 3 days and then measured using a semiconductor laser that emits at 800 nm. Exposure was performed by changing the light intensity at 1/100,000th of a second per pixel (100 microns).

Next, an automatic developing machine for X-ray manufactured by Konica Corporation (product name:
The film was processed for 45 seconds at a developing temperature of 35° C. using a Konica X-ray automatic developing machine (5RX-501). The processing liquid is Konica Corporation's X-ray automatic developing machine developer (product name: Konica XD-
3R) and a fixer (trade name: Konica It was exposed and developed in the same way.

Fog and sensitivity were evaluated for each sample after development. The sensitivity is determined by the common logarithm of the reciprocal of the exposure amount required to give a density of "fog + 1.0" for sample No. 1.
Table 1 shows the relative values when the sensitivity for 3 days at a temperature of 23° C. and a humidity of 55% RH is set as 100.

(Evaluation of remaining color) Each sample was subjected to the same treatment, and the remaining color after the treatment was visually evaluated. Evaluation was performed on the following five levels.

■Very poor 2 Inferior 3 Normal 4 Good 5 Very good The results obtained are shown in Table 1.

As is clear from Table 1 below, the samples of the present invention have improved storage stability under high temperature and high humidity conditions compared to the comparative samples, and have good performance with little brown residue.

〔Effect of the invention〕

As explained above, the silver halide photographic light-sensitive material of the present invention has the effects of improved storage stability under high temperature and high humidity conditions and less brownish residue.

Claims (1)

[Claims] It has at least one photosensitive silver halide emulsion layer that is spectrally sensitized to a wavelength range of 1,750 nm or more, and at least one of the photosensitive silver halide emulsion layers contains a spectral sensitizing dye and an iodide ion. 1. A silver halide photographic light-sensitive material comprising an emulsion to which is added a solution in which silver halide is dissolved.