JPH08122958A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain a photographic sensitive material high in sensitivity to laser beams in a red wavelength region by incorporating specified compounds in at least one of silver halide emulsion layers. CONSTITUTION: The silver halide photographic material having on a support at least one silver halide emulsion layer contains at least one of the compounds represented by formula I and at least one on the compounds represented by formula II. In formulae I and II, A1 is a 1-4C alkyl group; each of Z1 and Z2 is a nonmetallic atomic group necessary to form an optionally substituted benzene or naphthalene ring; each of R1 and R2 is a 1-4C lower alkyl group; X1 <-> is an anion group; P is 1 or 2; each or X3 and Z4 is a nonmetallic atomic group necessary to form an optionally substituted benzene or naphthalene ring; Z5 is a hydrocarbon group necessary to form an optionally substituted 6-membered ring; each of R3 and R4 is a 1-4C lower alkyl group; and X2 <-> is an anion group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and particularly to a red wavelength region (about 600 nm to about 600 nm).
The present invention relates to a silver halide photographic light-sensitive material having high sensitivity to a laser beam of 700 nm).

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials are required to have high sensitivity at different specific wavelengths depending on the purpose of use. As one of the production techniques for such a light-sensitive material, a certain sensitizing dye is added to a silver halide emulsion, and in a wavelength range longer than a specific light-sensing wavelength range of the silver halide, in a specific wavelength range. It is generally well known to effectively increase the sensitivity. Further, by using a certain sensitizing dye or an organic compound in combination with the sensitizing dye, the sensitizing dye or the compound imparts to the photographic emulsion more sensitivity than is recognized as the sum of the sensitivities imparted by each sensitizing dye or compound alone. It is known that this effect is called "supersensitization", and many combinations have already been reported. In recent years, it has been strongly desired that silver halide photographic light-sensitive materials have higher sensitivity, and it is important to develop a technique for efficiently performing spectral light enhancement. Therefore, in order to produce a highly sensitive light-sensitive material, it is extremely advantageous to use at least two kinds of sensitizing dyes which are in a supersensitizing relationship with each other and do not have a desensitizing effect in combination. Further, with the rapid development of optoelectronics in recent years, light sources such as laser light and LED light have been used in place of conventional incandescent light bulbs and the like as light sources that are used for image processing by electro-optically converting signal currents. Among them, the He-Ne laser, ruby laser, and red LED light, which are already in the practical range, have an emission wavelength in the range of 600 to 700 nm in the spectrum, and the light-sensitive materials for recording these red light have been conventionally proposed. The reality is that the combination of color sensitizations rarely satisfies the red light sensitivity. An object of the present invention is to provide a silver halide photographic light sensitive material having high sensitivity to laser light in the red wavelength region.

[0003]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is: This has been achieved by containing at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II].

[0004]

Embedded image

In the formula, A ₁ is a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-propyl group, iso
-Propyl group, n-butyl group, tert-butyl group, etc.),
Z ₁ and Z ₂ are each a substituent (eg, a halogen atom such as chlorine atom or bromine, a lower alkyl group having 1 to 4 carbon atoms such as methyl group and ethyl group, a lower alkyl group having 1 to 4 carbon atoms such as methoxy group and ethoxy group). Lower alkoxy group, phenyl group, trifluoromethyl group, etc.), a non-metal atom group necessary for forming a benzene ring or a naphthalene ring, R ₁ and R ₂ have ₁ to 4 carbon atoms
Lower alkyl group (eg, methyl group, ethyl group, n-
Propyl group, n-butyl group, iso-butyl group, etc.), a lower alkyl group having 1 to 4 carbon atoms having a sulfo group as a substituent (for example, sulfoethyl group, γ-sulfopropyl group,
γ-sulfobutyl group, δ-sulfobutyl group, etc.) and X ₁ ^- represent an anion group (eg, chlorine ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonate ion, etc.). p represents an integer of 1 or 2, and p is 1
When, an inner salt is formed.

[0006]

[Chemical 4]

In the formula, Z ₃ and Z ₄ are substituents (for example, a halogen atom such as chlorine atom and bromine, a lower alkyl group having 1 to 4 carbon atoms such as methyl group and ethyl group, a methoxy group and an ethoxy group). A non-metal atom group necessary for forming a benzene ring or a naphthalene ring which may have a lower alkoxy group having 1 to 4 carbon atoms, a phenyl group, a trifluoromethyl group, etc.,
Z ₅ is a hydrocarbon group necessary for forming a 6-membered ring which may have a substituent (for example, a lower alkyl group having 1 to 4 carbon atoms such as a methyl group), R ₃ and R ₄ are carbon atoms 1 to 4 lower alkyl groups (eg, methyl group, ethyl group, n-propyl group, n
-Butyl group, iso-butyl group, etc.), a lower alkyl group having 1 to 4 carbon atoms and having a sulfo group as a substituent (for example, sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, etc.) , A lower alkyl group having 1 to 4 carbon atoms having a phenyl group as a substituent (for example, benzyl group, phenethyl group, etc.), X ₂ ^- is an anion group (for example, chlorine ion, bromide ion, iodine ion, perchlorate ion) , P-toluenesulfonate ion). q represents an integer of 1 or 2, and when q is 1, it forms an inner salt. The following compounds may be mentioned as specific examples of the compounds represented by the above general formulas [I] and [II].

[0008]

Embedded image

[0009]

[Chemical 6]

[0010]

[Chemical 7]

[0011]

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[0012]

[Chemical 9]

[0013]

[Chemical 10]

[0014]

[Chemical 11]

The compound represented by the general formula [I] or [II] can be synthesized by a known method. For example, US Patent No. 2503776, British Patent No. 742112, and
595784, US Pat. No. 2,734,900, and Frances M. Harmer, THE CYANINE DYES AND RELATED COMPOUNDS, INTERCIENCE・ Publishers (INTERSCIENCE PU
BLISHERS), 1964. General formula [I]
The addition amount of the compound represented by the above is in the range of 20 to 500 mg, preferably 100 to 300 mg, based on 1 mol of silver halide. The addition amount of the compound represented by the general formula [II] is 1 to 100 mg, preferably 10 to 50, based on 1 mol of silver halide.
The range is mg. To use the compound represented by the general formula [I] or [II] in a silver halide emulsion, the compound is added and dissolved in the emulsion, or water or an organic solvent such as methanol, ethanol or acetone, or a mixture thereof is used. It may be added after being dissolved in a solvent. At this time, the compounds of the general formula [I] or [II] may be mixed and added, or may be added individually in any order. The compound represented by formula [I] or [II] may be added to the silver halide emulsion before chemical sensitization, during chemical sensitization, or after chemical sensitization.

The silver halide emulsion used in the present invention is
The ratio of silver chloride, silver bromide, and silver iodide is not limited, but silver chlorobromide and silver iodochlorobromide in which 50 mol% or more of silver halide is silver chloride, particularly 60% or more It is preferably composed of silver. The silver halide grains used in the present invention are preferably cubic crystals and monodisperse. The fact that the silver halide grains are substantially cubic and monodisperse means that from a perfect cubic crystal in which all crystal surfaces are [100] faces, [100] faces are 70% or more,
Preferably, it occupies 80% or more, and the other is [111] plane 14
Consist of silver halide crystals containing a faced crystal and having a diameter or proportion of grains, which accounts for 80%, preferably 90% or more of the total weight or number of silver halide grains, is within ± 40% of the average grain size. Is. The average grain size of the silver halide grains is preferably 0.7 μm or less. For more information on determining the average particle size, see THE THEORY OF THE PHOTOPGRAP by CEMees and THJames.
HIC PROCESS), 3rd edition, pp. 36-43, 1966, published by MACHILLAX. The substantially cubic and monodisperse silver halide emulsion used in the present invention is a mixture of a soluble silver salt and a soluble halogen salt at the same time to keep the pAg in the liquid layer in which silver halide is formed constant. It can be created by the controlled double jet method. Regarding this controlled double jet method, for example, PHOTOGRAPHIC SCIENCE (PHOTOGRAPHIC SCIENCE
AND ENGINEERING), Vol. 5, pp. 332-336, 1961.

As the silver halide binder or protective colloid used in the present invention, it is advantageous to use gelatin, but other gelatins such as gelatin derivatives can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of gelatin derivatives include, for example, US Pat.
The reaction product of gelatin with an acid anhydride, an isocyanate, or a compound having an active halogen, which is described in Japanese Patent No. 928 and JP-A-46-5182, can be mentioned. Examples of the acid anhydride used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, succinic anhydride, and the like. Examples of the isocyanate compound include phenyl isocyanate and p -Bromophenyl isocyanate, p-chlorophenyl isocyanate, p-tolyl isocyanate, p
Examples thereof include nitrophenyl isocyanate and naphthyl isocyanate.

Examples of the compound having an active halogen include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, naphthalene-β-sulfonyl chloride, Examples thereof include m-carboxybenzenesulfonyl nechloride, 2-amino-5-methylbenzenesulfonyl chloride, ethylchlorocarbonate and 2,4-dichloro-6-hydroxy-s-triazine sodium salt.

The silver halide photographic emulsion used in the present invention usually removes soluble salts after the formation of precipitates or after physical ripening. As a means therefor, a Nudel washing method in which gelatin is gelled, a polyvalent anion is used. Inorganic salts (for example, sodium sulfate), anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid), gelatin derivatives (aliphatic acylated gelatin,
A precipitation method (flow curation) using aromatic acylated gelatin, aromatic carbamoylated gelatin, etc. may be used.

The silver halide photographic emulsion used in the present invention is preferably sensitized with a sulfur sensitizer containing unstable sulfur. Examples of the sulfur sensitizer include thiourea, allyl isothiocyanate, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate. Particularly, sodium thiosulfate is preferable.

The silver halide photographic emulsion used in the present invention includes an antifoggant (for example, benzotriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, etc.), filter dye, organic or inorganic hardener ( For example, chromium alum, formaldehyde, glyogizal, 2,4-dichloro-6-hydroxy-s-triazine / sodium, etc.), a surfactant, a water-insoluble or sparingly soluble polymer latex, etc. can be contained.

Examples of the support used in the present invention include cellulose acetate film, polyethylene film, polypropylene film, polystyrene film, polyethylene paper, paper coated with a resin such as polyethylene, and synthetic paper.

For the photographic processing of the silver halide photographic light-sensitive material of the present invention, known methods can be used. The processing temperature is usually in the range of 18 to 45 ° C. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-Pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-3-aminophenol) and the like can be used. The developer contains other known preservatives, alkali agents, pH buffers, antifoggants, etc., and further contains a dissolution aid, a color tone agent,
A development accelerator, a surfactant, a defoaming agent, a water softening agent, a film hardening agent, a viscosity imparting agent and the like may be contained. The fixing agent may have a known composition. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds to which an effect as a fixing agent is added can be used. The fixing solution may contain a water-soluble aluminum compound as a hardening agent.

[0024]

【Example】

Example 1 <Preparation of silver chlorobromide emulsion> Solution (A) Gelatin 27 g Distilled water 1200 ml Sodium chloride 1.2 g Sodium benzenesulfinate 1.5 g Salicylic acid (20% methanol solution) 5 ml 1,8-dihydroxy-3, 6-dithiaoctane (1% aqueous solution) 7 ml solution (B-1) Silver nitrate 30 g Make up to 200 ml with distilled water. Solution (C-1) Sodium chloride 6.2 g Potassium bromide 8.4 g Rhodium trichloride (0.02% aqueous solution) 0.3 ml Make up to 200 ml with distilled water. Solution (B-2) Silver nitrate 150 g Make up to 700 ml with distilled water. Solution (C-2) Sodium chloride 31.0 g Potassium bromide 42.0 g Hexachloroiridium (IV) dipotassium salt (0.2% aqueous solution) 1.0 ml Make up to 700 ml with distilled water. Solution (B-1) and solution (C-1) were stirred while keeping pH at 3 and pAg at 8 at solution (A).
Are simultaneously added over 30 minutes, and the mixture is stirred for 5 minutes, and then the solution (B-2) and the solution (C-2) are further mixed under stirring for 50 minutes.
Added over minutes. After stirring for 5 minutes, the temperature was lowered to 25 ° C and 2 ml of caustic soda (10% aqueous solution) was added.
40 ml of magnesium sulfate (20% aqueous solution) was added. After stirring for 2 minutes, 10 ml of sulfuric acid (6N) was added, decantation was performed, and further washing with water was performed. Add 20 ml of distilled water to the above emulsion.
0 ml and 18 g of gelatin were added and dispersed at 50 ° C for 30 minutes.
Next, after adding 13 ml of potassium bromide (10% aqueous solution) and caustic soda (10% aqueous solution) to adjust the pH to 6.0 and pAg7.0,
6.0 ml of sodium thiosulfate (0.1% aqueous solution) and 10 ml of chloroauric acid (0.1% aqueous solution) were added, and the mixture was aged at 60 ° C for maximum sensitivity. The emulsion was divided and the sensitizing dye was added in a methanol solution as shown in Tables 1 and 2. After keeping at 40 ° C for 20 minutes, 0.6 g of 1-phenyl-5-mercaptotetrazole (0.5% methanol solution) was added per 4 g of silver nitrate.
l, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (1% methanol solution) 1 ml, ethylenediaminetetraacetic acid (5% aqueous solution) 0.5 ml, saponin (10% aqueous solution) 1 ml , 30 ml of gelatin (10% aqueous solution) was added.

[0025]

[Chemical 12]

<Preparation of protective layer> 20 g of gelatin was added to 50 parts of distilled water.
After dissolving in 0 ml, 15 ml of saponin (10% aqueous solution) and 5 ml of dioctyl succinate sodium salt (mixed solution of 5% isopropyl alcohol and water) were added. <Preparation of sample> Formalin was added to the above silver chlorobromide emulsion,
Two layers were simultaneously coated on a polyethylene-coated paper provided with a gelatin subbing layer together with the above-mentioned protective layer, and dried to prepare a sample.
The emulsion layer was coated so that the silver coating amount was 1.5 g per 1 m ² , and the protective layer was coated so that the gelatin amount was 1.0 g per 1 m ² . <Evaluation of image> This sample was attached to a xenon flash (10 ^-5 with a red filter (Ratten No. 29) under a light wedge.
Second) and exposed to an automatic processor using the following developer and fixer for development and fixing at 32 ° C. for 30 seconds, water washing at room temperature for 30 seconds, and drying at 50 ° C. for 20 seconds. Developer Potassium sulfite (55% w / v aqueous solution) 126 ml Ethylenediaminetetraacetic acid tetrasodium salt 0.4 g Potassium hydroxide (48.5% w / v aqueous solution) 12.8 ml Potassium bromide 3.3 g Diethylene glycol 50 ml Hydroquinone 20 g Potassium carbonate (anhydrous) ) 23.3 g potassium hydroquinone sulfonate 1.7 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1.0 g 5-methylbenzotriazole 0.2 g 3,3'-dithio-bishydrocinnamic acid 1.3 g dioctylsulfo Succinate sodium salt (5% w / v aqueous solution) 0.1 ml 1-phenyl-5-mercaptotetrazole (2% w / v methanol solution) 1.0 ml Pure water is added to bring the total volume to 1000 ml. pH = 11.0 Fixer Ammonium thiosulfate (70% w / v aqueous solution) 180 ml Sodium sulfite (anhydrous) 15 g Sodium thiosulfate (anhydrous) 10 g Boric acid 6.7 g Tartaric acid 1.0 g Sodium hydroxide 4.0 g Acetic acid (90% aqueous solution) 11.3 ml Ethylenediaminetetraacetic acid disodium salt 0.1 g Potassium alum 10 g Add pure water to make the total volume 1000 ml. pH = 4.8 The results are shown in Tables 1 and 2. The sensitivities in Tables 1 and 2 are represented by the reciprocal of the exposure amount that gives the minimum density (fog) +0.6, and the relative sensitivity with the sensitivity of Sample 8 being 100. From the results of Tables 1 and 2, comparative samples 1 to 4, 8, and 12
In comparison with Samples 5-7, 9-11, 13-15, 16-33 of the present invention
It can be seen that has a high sensitivity. Further, it is understood that the samples 34 to 42 of the combination other than the present invention have lower sensitivity than the samples of the present invention.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

According to the present invention, a silver halide photographic light-sensitive material having a high sensitivity to laser light in the red wavelength region can be obtained.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers contains at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. Silver halide photographic light-sensitive material. Embedded image (In the formula, A ₁ is a lower alkyl group, Z ₁ and Z ₂ are non-metal atom groups necessary for forming a benzene ring or a naphthalene ring which may have a substituent, and R ₁ and R ₂ are substituents. sulfo group lower alkyl group which may have as, X ₁ ^-. the .p representing the anionic group is an integer of 1 or 2, in which p forms an intramolecular salt when 1) ## STR2 ## (In the formula, Z ₃ and Z ₄ are non-metal atom groups necessary for forming a benzene ring or a naphthalene ring which may have a substituent,
Z ₅ represents a hydrocarbon group necessary for forming a 6-membered ring, R ₃ and R ₄ represent a lower alkyl group which may have a sulfo group or a phenyl group as a substituent, and X ₂ ⁻ represents an anion group. q represents an integer of 1 or 2, and when q is 1, it forms an inner salt. ) 2. The silver halide photographic light-sensitive material according to claim 1, which is for a red laser light source.