JPH05303158A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in sensitivity and contract in a red color wavelength region and small in fog and residual color after processing. CONSTITUTION:The silver halide photographic sensitive material contains at least one of photosensitive layers comprising a silver halide emulsion prepared by adding a cationic tricyclic cyanine dye stuff represented by formula I to a cubic silver halide emulsion composed essentially of silver bromide mixed by a double jet method in a condition of pAg>=8.5. In formula I, each of Z and Z1 is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring usually used in the cyanine dyes stuff, each of R and R1 is a saturated or unsaturated aliphatic group; each of Q and Q1 is an atomic group necessary to form a 4-thiazolidinone or 5-thiazolidinone or to form 4-imidazolidinone nuclean, each of L1-L3 is methine or substitute methine group, each of (L1 and R) and (L3 and R1) may combine through a methylene group to form an N- containing hetero ring; each of m and n is 0 or 1; and X is an anion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and in particular, it has high spectral sensitivity in the red light region, high sensitivity, high contrast, low fog, and residual after processing. The present invention relates to a silver halide light-sensitive material having less color.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are required to have sensitivities at different specific wavelengths depending on their purposes. It is generally well known as one of the techniques for producing such a light-sensitive material that certain sensitizing dyes are added to silver halide to effectively enhance the sensitivity at a specific wavelength.

With the rapid development of optoelectronics in recent years, light sources such as laser light and LED light have begun to be used as a light source for outputting digitized image information in place of a conventional incandescent light bulb. Among them, He-Ne laser light, ruby laser, red L that is already in the practical range
The ED light has an emission wavelength in the range of 600 to 700 nm, and silver halide light-sensitive materials for recording these red lights have been widely used.

To manufacture such a light-sensitive material, sensitizing dyes having a spectral maximum in the red light region are added to a silver halide photographic emulsion. As typical ones, many ones such as cyanine dyes and merocyanine dyes have been proposed, and JP-B-49-13331 and JP-A-50-
It is known that trinuclear dyes such as those disclosed in No. 62425 and British Patent No. 1471701 are also very effective in enhancing such red light sensitivity. However, these sensitizing dyes, while increasing the red light sensitivity of the silver halide photographic emulsion, have problems such as increased fog and a large amount of residual color after processing.

The recorded silver halide light-sensitive material has a reduced commercial value if it is fogged or colored, or is used as a document for printing on a printing plate such as a PS plate or as an original for photographing with a camera in the next step. Not desirable for performance.

Accordingly, there is a demand for a silver halide photographic light-sensitive material which has high sensitivity to such a red light source, has little fog, and has no residual color of dye after processing.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity and high contrast in the red wavelength region, less fog and less residual color after processing.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to prepare a cubic silver halide emulsion mainly composed of silver bromide, which is mixed by the double jet method, under the condition of pAg of 8.5 or more, to obtain the cationic trisodium compound represented by Chemical formula 1. It could be achieved by a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a silver halide emulsion to which a nuclear cyanine dye is added.

In the chemical formula ₁ , Z and Z ₁ each represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocycle usually used in cyanine dyes. Examples of the above heterocyclic nucleus include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, 2
-Quinoline nucleus, 4-quinoline nucleus, 2-pyridine nucleus, 4-
Pyridine nucleus, 3,3-dialkylindolenine nucleus, benzimidazole nucleus, etc., wherein the carbon atom of this heterocycle has a substituent such as a halogen atom, an alkyl group, an alkoxyl group, a hydroxy group or a monoaryl group. Good.

R and R1 are each a saturated or unsaturated aliphatic group such as a lower alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), such as an alkoxy group, an alkoxycarbonyl group. A substituted alkyl group having a substituent such as a vinyl group or a monoaryl group (preferably one having an alkyl radical having 5 or less carbon atoms)
Represents.

Q and Q1 (combination) represent a group of atoms necessary for forming a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus.

[0012] Represents a lower alkyl group or an aryl group. )
Represents.

L1 and R, and L3 and R1 may be bonded to each other by a methylene chain to form a nitrogen-containing heterocycle.

M and n represent 0 or 1.

X represents an anion such as chlorine ion, bromine ion, iodo ion, P-toluenesulfonate ion and the like.

In the present invention, the sensitizing dye is added under the condition of pAg of 8.5 or more means that the pAg is 8.5 or more at the time of adding the sensitizing dye. It includes the case where the sensitizing dye is adjusted to have a pAg or more after the addition, and in any case, the state is maintained even when the emulsion is coated.

To adjust the pAg of the emulsion, water-soluble halides such as potassium bromide, sodium bromide, ammonium bromide, potassium chloride, sodium chloride, ammonium chloride, and in some cases, water-soluble silver salts such as silver nitrate. Can be used.

The silver halide used in the present invention is cubic silver halide mainly composed of silver bromide. The term "mainly containing silver bromide" means that the content of silver bromide in one grain of silver halide is 70 mol% or more, preferably 90 mol% or more. Silver chlorobromide or silver chloride having a lower silver bromide content is generally low in sensitivity and easily fogged, which is inconvenient for the purpose of the present invention. Further, it is difficult to obtain high-sensitivity and high-contrast properties with octahedral grains, and in order to achieve the object of the present invention, cubic bromide grains mainly composed of silver bromide, especially crystal habit mixed by the double jet method, are used. It is necessary to use uniform silver halide grains.

The addition amount of the sensitizing dye of Chemical formula 1 used in the present invention is in a wide range from 5 mg to 500 mg per mol of silver halide, and the optimum amount for obtaining the effect can be arbitrarily selected. These sensitizing dyes may be used alone, or may be used in combination.

In order to add the sensitizing dye to these silver halide emulsions, it is possible to add it as a solution of a solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide, and water alone or in a mixture.
It can also be incorporated into the emulsion using ultrasonic dispersion. Further, US Pat. Nos. 3,482,981 and 358.
No. 5195, No. 3469987, No. 364928
No. 6, No. 3485634, No. 3342605,
Also, the method described in Japanese Patent No. 2912343 can be used.

The sensitizing dye may be added to the silver halide photographic emulsion at any time during the emulsion manufacturing process.

Next, specific examples of the sensitizing dye used in the present invention are listed, but the sensitizing dye used in the present invention is not limited thereto.

[0022]

[Chemical 2]

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

[0048]

[Chemical 28]

[0049]

[Chemical 29]

[0050]

[Chemical 30]

[0051]

[Chemical 31]

[0052]

[Chemical 32]

[0053]

[Chemical 33]

[0054]

[Chemical 34]

[0055]

[Chemical 35]

[0056]

[Chemical 36]

The sensitizing dye used in the present invention is Francis. M. By Frances.M.Hamer The cyanine dyes and related compounds, John Wiley and Sons Limited
Sons Ltd) (1964), German Patent No. 97194
It can be easily synthesized by a person skilled in the art by referring to Nos. 1 and 1013167 and US Pat. No. 29476.

The silver halide photographic emulsion used in the present invention is an emulsion composed of substantially cubic silver halide grains prepared by the double jet method. Substantially means, on average, particles produced under the condition that cubic particles are predominantly formed, and there is a slight distribution of crystal habits, and abnormal particles and cubic vertices and edges are rounded. It does not matter if there are particles. PAg and p during double jet mixing
Conditions such as H may or may not be controlled so as to maintain a constant value, but it is desirable that they be controlled.

The silver halide grains may have different phases in the inside and the surface layer, or may have a uniform phase.

Further, for example, a composite type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, or an epitaxially grown silver halide crystal (for example, It is also possible to epitaxially grow silver chloride, silver iodobromide, silver iodide, etc. on silver bromide).

The grain size and distribution of the silver halide grains used in the present invention are arbitrary, but they are preferably monodisperse. Here, the monodispersion means that 95% of particles are within ± 60% of the number average particle size, preferably 40%.
It is a dispersed system that falls within the size of%. Here, the number average grain size is the number average diameter of the projected area diameters of the silver halide grains.

Further, two or more kinds of silver halide emulsions formed separately may be mixed.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, and the like may coexist.

As the method for removing the soluble salts from the emulsion after the formation of the precipitate or after the physical preparation, the noodle method for gelling gelatin, inorganic salts, anionic surfactants, anionic polymers or modified gelatin are used. The precipitation method (flocculation method) or the like is used.

The silver halide emulsion can be chemically sensitized by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine, and rhodanine, and US Pat.
No. 278947, No. 2410689, No. 244020
No. 6, No. 3187458, No. 3415649, No. 3
Sulfur-containing compounds such as those described in No. 501313 can be used. Also, US Pat.
Gold sensitization can be carried out with the gold compounds described in JP-A Nos. 2597915 and 2599083.
In addition, US Pat.
No. 2556245 and No. 2566263, the sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium and ruthenium can be used in combination. And these sensitization methods can be used not only in combination but also in combination.

In the present invention, polyalkylene oxide,
Various development accelerators such as thioether compounds and quaternary ammonium salt compounds can be used.

The silver halide photographic emulsion used in the present invention may optionally contain other sensitizing dyes such as cyanine,
Spectral sensitization may be carried out by using merocyanines in combination, and addition of stabilizers, surfactants, hardeners and the like may be added by known methods.

Examples of the hydrophilic colloid used in the present invention include proteins such as gelatin, colloidal albumin and casein, cellulose derivatives such as carboxymethyl cellulose, agar, sodium alginate, sugar derivatives such as starch, polyvinyl alcohol and polyacrylamide. These synthetic polymers and the like can be used alone or in a mixture at an appropriate ratio.

In the light-sensitive material of the present invention, all the materials usually used as a support for a photographic light-sensitive material are used. Examples thereof include cellulose nitrate film, cellulose acetate film, cellulose acetate propylate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film and other laminates thereof, and paper. Also suitable are supports such as baryta or paper coated with or laminated with an α-olefin polymer, particularly a polymer of α-olefin having 1 to 10 carbon atoms such as polyethylene, polypropylene.

[0070]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the description.

Example 1 By the control double jet method, pAg = 7.
A cubic silver iodobromide emulsion containing 1.0 mol% of silver iodide and having an average particle size of 0.3 μm was prepared under the conditions of pH = 4.5. This emulsion was washed with water for precipitation by an ordinary flocculation method, then subjected to gold-sulfur sensitization, and 7-hydroxy-5-methyl-1,3,4,7a-tetrazaindene was added as a stabilizer. When the pAg of the emulsion was measured here, it was about 8.0. Divide this emulsion into Table 1
After adjusting the pAg as shown in, the sensitizing dyes shown in the table were added. Further, an antifoggant, a coating aid and a hardener which are commonly used are added to obtain a finished emulsion.

Further, a coating aid and a hardener were added to a 5% gelatin aqueous solution to prepare a coating over liquid.

These coating emulsions and coating over liquids were coated on 100 μm-thick photographic polyethylene-coated paper with a coating emulsion layer having a coating silver amount of 1.8 g / m ² and an over layer having a gelatin coating amount of 1.5 g after drying. Two layers were simultaneously coated by a slide hopper coating method so as to be / m ² and dried to obtain a sample.

This sample was subjected to wedge exposure by using a sensitometer having a light source with a color temperature of 5400 ° K, and attaching an interference filter for transmitting light of 633 nm to the light source. Successively, each sample was processed with an automatic processor to develop developer M manufactured by Mitsubishi Paper Mills Co., Ltd.
Development was carried out at 38 ° C. for 20 seconds using RA-CD231, fixing was carried out using fixing solution MRA-CF801 manufactured by Mitsubishi Paper Mills Ltd., and further washing with water was carried out to obtain strips having a predetermined black and white image.

The density of the sample was measured using a MACBETH TD-504 densitometer manufactured by Macbeth Corporation in the United States to obtain red light sensitivity. The reference point of the optical density at which the sensitivity was determined was 0.75 in all cases. After the unexposed sample was developed at 38 ° C. for 60 seconds, the fog density was measured.

The results are shown in Table 1. Sensitivity is 38 ℃ 20
It is a value when the second development processing is performed, and is shown as relative sensitivity with Samples 1 and 5 as 100. The addition amount of the sensitizing dye is the addition amount (mol) per mol of silver. Further, regarding the dye loss, the degree of coloring in the case of development processing at 38 ° C. for 20 seconds was evaluated by 5 grades, with 1 being the one having no coloring at all. No. 2 is only slightly colored, and No. 4 or more is the degree of coloring that is serious and is a problem in practical use.

[0077]

[Table 1]

[0078]

[Chemical 37]

[0079]

[Chemical 38]

As is clear from Table 1, according to the present invention, it is possible to obtain a light-sensitive material having high sensitivity, low fog, and little residual color due to a dye after processing.

Example 2 An emulsion was prepared in the same manner as in Example 1 except that the types and addition amounts of sensitizing dyes were as shown in Table 2, and the polyethylene-coated paper was prepared in the same manner as in Example 1. 2 layers were simultaneously coated on the above and developed. The sensitivity and the like after the development processing were also measured by the same method as in Example 1.

The results are shown in Table 2. The values of sensitivity in the table are shown as relative values when the result of Sample No. 1 is 100.

[0083]

[Table 2]

[0084]

[Chemical Formula 39]

As described above, it is understood that the product of the present invention has high sensitivity, low fog, and very little residual color after processing.

[0086]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide light-sensitive material having a maximum spectral sensitivity in the red light region and used in a system including a step of exposing mainly using He-Ne laser light, has a sensitivity in the red wavelength region. It is possible to obtain an excellent light-sensitive material having a high color tone, a high contrast, little fog, and less residual color after processing.

Claims (1)

[Claims] 1. A halogenated compound in which a cationic trinuclear cyanine dye represented by Chemical formula 1 is added to a cubic silver halide emulsion mainly composed of silver bromide mixed by a double jet method under the condition of pAg of 8.5 or more. A silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a silver photographic emulsion. [Chemical 1] In Chemical Formula ₁ , Z and Z ₁ each represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring which is usually used in cyanine dyes. R and R1 each represent a saturated or unsaturated aliphatic group. Q and Q1 (combination) represent a group of atoms necessary to form a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus. L1, L
2, L3 represents a methine group which may have a substituent. Further, L1 and R, and L3 and R1 may be bonded with a methylene chain to form a nitrogen-containing heterocycle. m and n represent 0 or 1. X represents an anion.