JPS6046695B2 - silver halide photographic emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to spectrally amplified silver halide photographic emulsions, particularly silver halide photographic emulsions containing specific cyanine dyes.

As is well known, adding a mulching dye to a silver halide emulsion expands the sensitive wavelength range of the silver halide emulsion and optically sensitizes it.

Many sensitizing dyes used for this purpose have been proposed. For example, in ``The Theory of the Photographic Process'' by C.E., Mies and T.H. James.
tographicProcess Month (3rd edition) 196
6 years McClammin, Co., N. Y) pp. 198-22
Examples include cyanine dyes, merocyanine dyes, xanthine dyes, etc. described on page 8. When these mulching dyes are applied to silver halide emulsions, they must satisfy not only the expansion of the sensitive wavelength range but also the following requirements. That is, (1) the spectral sensitization range is appropriate (2) there is no adverse effect due to other photographic additives such as stabilizers, coating aids, gala couplers, etc. (3) the silver halide emulsion is being stored (4) No fogging should occur (5) The multiplying dye should not diffuse into other photosensitive layers and should not cause a decrease in sensitivity during storage, especially under conditions of high temperature and high humidity. (6) No residual coloration, etc., should not occur.

Incidentally, in recent years, it has been desired to spectrally sensitize the blue sensitivity region of a silver halide emulsion to an appropriate sensitivity region, regardless of the inherent sensitivity region of the silver halide emulsion.

This is particularly important for improving color reproducibility in multilayer color photographic materials. Moreover, with the increase in sensitivity in the green and red regions of multilayer color photographic materials, the developability of blue-sensitive emulsions containing yellow couplers becomes uneven, making it difficult to obtain color balance due to color reproducibility. , it has become necessary to increase the sensitivity in the blue region. Sensitizing dyes for this purpose include the simple merocyanine dyes described in U.S. Pat. Specification, JP-A-48-78
Monomethine cyanine dyes described in Japanese Patent No. 930 and the like are known. However, conventionally known simple merocyanine dyes have the drawback that the spectral sensitivity distribution of the silver halide emulsion is broad and extends to the long wavelength side, and is amplified to the green region. This deteriorates the color reproducibility of multilayer color photographic materials. In addition, monomethine cyanine dye is
Although it generally provides an appropriate blue sensitivity range, it has the disadvantage of large residual coloring. An object of the present invention is to avoid contamination of processed photographic materials due to residual coloring. This provides a silver halide photographic emulsion that is spectrally amplified to a suitable blue sensitivity range. Another object of the present invention is to provide a silver halide photographic emulsion with highly increased sensitivity in the blue region.

Another object of the present invention is to provide a highly sensitive multilayer color photographic material with good color reproducibility.

This object of the present invention can be achieved by incorporating a mulching dye represented by the following general formula into a silver halide emulsion. In the general formula, one of R1 and R2 is a sulfoalkyl group (e.g., 2-sulfoethyl group, 2-sulfopropyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4
-sulfobutyl group) or carboxyalkyl group (e.g. 2-carboxyethyl group, 2-carboxypropyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.), the other Aralkyl groups (for example, unsubstituted aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, or aralkyl groups having substituents such as trimethyl group, tolylethyl group, tolylpropyl group, P-methoxyphenylethyl group) , except those substituted with a sulfo group or a carboxyl group) or phenoxyalkyl groups (for example, unsubstituted phenoxy groups such as 2-phenoxyethyl group, 3-phenoxypropyl group, 3-phenoxybutyl group, and 4-phenoxybutyl group) Alkyl group or 2-(P
-methyl)phenoxyethyl group, 3-(P-methoxy)
phenoxyalkyl group having a substituent such as phenoxypyrobyl group, 4-(P-methoxy)phenoxybutyl group,
(excluding those substituted with sulfo or carboxyl groups).

Z1 and 4 are 5- or 6-membered heterocyclic nuclei (e.g., pyrroline, indoline, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, imidazole) , benzimidazole, pyridine, 2-quinoline, 4
-quinoline, 1-isoquinoline, 3-isoquinoline, etc.)
represents a group of nonmetallic atoms necessary to form Benzothiazole, 6-chlorobenzothiazole, 5-bromobenzothiazole, 6
-bromobenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-chlorobenzoselenazole, 6-chloro-2-quinoline, 8
-chloro-2-quinoline, 8-chloro-4-quinoline,
1-aryl-5,6-dichlorobenzimidazole, etc.), a heterocyclic nucleus substituted with an alkyl group (e.g., 4-
Methylthiazole, 5-methylthiazole, 4,5-dimethylthiazole, 4-methylbenzothiazole, 5-
Methylbenzothiazole, 6-methylbenzothiazole, 4-methyloxazole, 5-methyloxazole,
4-ethyloxazole, 4●5-dimethyloxazole, 5-methylbenzoxazole, 6-methylbenzoxazole, 4●6-dimethylbenzoxazole,
4-methylselenazole, 4-methylthiazoline, 5-
Methyl-2-pyridine, 3-methyl-4-pyridine, 3
-methyl-2-quinoline, 5-ethyl-2-quinoline,
7-Methyl-4-quinoline, 3,3″-dimethylindoline, 3●3●5-trimethylindoline, 1-ethylimidazole, 1-methyl-1H-naphtho[12-d]
imidazole, 1-methyl-5-methoxy 1H-naphtho[1◆2-d]imidazole, 1-methylbenzimidazole, etc.), heterocyclic nuclei substituted with alkoxy groups (
4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole,
5●6-dimethoxypenzothiazole, 5-methoxynaphtho[2●3-d]thiazole, 5-ethoxynaphtho[
2・3-d] Thiazole, 8-methoxynaphtho [2●3
-d] Thiazole, 7-methoxynaphtho [2,3-d]
Thiazole, 4″-Methoxythianafuceno 7″/6″
・4,5-thiazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoselenazole, 6-methoxy2-quinoline, 8-ethoxy2-
quinoline, 6-methoxy-4-quinoline, etc.), heterocyclic nuclei substituted with hydroxyl groups (e.g. 5-hydroxybenzothiazole, 6-hydroxybenzothiazole,
5-hydroxybenzoxazole, 6-hydroxybenzoxazole, 5-hydroxybenzoselenazole, 8-hydroxy-2-quinoline, 3●4-dihydroxy-1-isoquinoline, etc.), heterocyclic nuclei substituted with aryl groups (e.g., 5- Phenylthiazole, 4,5-
Diphenylthiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 4-phenyloxazole, 4,5-diphenyloxazole, 5-phenylbenzoxazole, 4-phenylselenazole, 1
-phenylbenzimidazole, 1-phenyl-naphtho[1,2-d]imidazole, etc.), heterocyclic nuclei substituted with a thinyl group (e.g. 4-(2-thynyl)thiazole, etc.), dialkylamino group-substituted Heterocyclic nucleus (
For example, 5-dimethylamino-2-quinoline, 6-dimethylamino-2-quinoline, etc.). X represents an acid anion group (eg, chloride ion, bromide ion, iodide ion, perchlorate ion, valatoluenesulfonic acid, ethyl sulfate ion, etc.). n represents an integer of 1 or 2, and when n is 1, an inner salt is formed. Typical specific examples of the mulching dye represented by the above general formula include the following.

However, the sensitizing dyes used in the present invention are not limited to these. Sensitizing dye NO. These sensitizing dyes can be easily synthesized by referring to the manufacturing methods described in US Pat. No. 3,149,105, British Patent No. 660,408, and British Patent No. 7,421P.

The sensitizing dye used in the present invention is about 1 x 10-5 mol to 2 x 10-3 mol per mol of silver halide in the silver halide emulsion.
Molar concentrations are advantageously used. Further, a conventional method can be used to add such a sensitizing dye to a silver halide emulsion. For example, a method in which a sensitizing dye is dissolved in a water-compatible organic solvent such as acetone, methanol, ethanol, propanol, methyl cellosolve, pyridine, dimethylformamide, etc. and added to an emulsion, or as described in U.S. Pat. No. 3,469,987. As described in JP-A No. 50-114, a method of dissolving a brightening dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, and then adding this dispersion to an emulsion, As described in the publication, a color enhancer is dissolved in an organic solvent that is compatible with water, and this solution is mixed and dissolved in water or a hydrophilic colloid solution containing an anionic surfactant. Other methods include methods of adding the compound to the emulsion, as well as methods described in U.S. Pat. No. 2,912,345, U.S. Pat. No. 3,342,605, U.S. Pat. These sensitizing dyes may be added to the emulsion at any step before coating on the support, but it is convenient to add them after the completion of the second ripening and prior to coating on the support. The silver halide photographic emulsion used in the present invention includes, for example, coarse grains (average grain size of 0.3 microns or more) of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or Fine particles (average particle diameter of 0.3 microns or less) or ultrafine particles (a). (average particle diameter of 0.05 microns or less) or mixed particulate silver halide crystals with a binder such as gelatin, acid-treated gelatin, gelatin derivatives such as acylated gelatin, phthalated gelatin, albumin, agar, gum arabic, Silver halide emulsions are dispersed in alginic acid, hydrophilic resins such as polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives, etc., or combinations of two or more thereof, or water-insoluble resins such as polyvinyl butyral. Or manufactured by double jet method.

These methods are described in "Photographic Chemistry" P
Written by ierre Glafides, FOuntainPr
ess. sLOndOn (1958) pp. 327-3
Page 30: “Nucleati in Silver Bromide Precipitation”
OninSilverBrOmidePrecipit
atiOn)”C. R. Berry and P. C. Sk
Co-authored by iiiman; J. Phys. Chem. , No. 68
Volume, pp. 1138-1143 (196 poems) “The Theory of the Photographic Process (
TheOryOfllePhOtOgr'Ap
hjcPrOcess)” (3rd edition), C. E. K. M
ees and T. H. Co-authored by John James (1966), page A, etc. The silver halide emulsion used in the present invention is preferably an ordinary surface latent image type emulsion, but internal latent image emulsions obtained by the so-called "conversion method" as described in U.S. Pat. No. 3,622,318 are suitable. It can also be applied to emulsions made by chemically sensitizing image-type emulsions to make the surface highly sensitive.

It can also be applied to internal latent image type emulsions. These silver halide emulsions can be prepared using commonly used chemical sensitization methods, such as U.S. Pat.
Chemical sensitization method using natural active gelatin or sulfur compound described in each specification of 1068 Wani, US Patent No. 2448
Chemical sensitization method using noble metal compounds such as ruthenium, rhodium, palladium, iridium, or platinum described in the 06-2001 specification, US Pat. No. 2,399,083, US Pat. No. 2,642
Chemical sensitization method using gold salts (potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, auric trichloride or 2-oresulfobenzothiazole methochloride) described in each specification of No. 361, US Pat. No. 2,487,850 Chemical sensitization is carried out by a chemical sensitization method using a reducing agent such as polyamines as described in the specification of US Pat. It may be something that is felt or something that is not. Silver halide emulsions according to the invention may contain commonly used yellow couplers.

As the yellow coupler, for example, a compound that forms a yellow dye by reacting with the oxide of a color developing agent having a primary amino group, such as an open-chain ketomethylene compound such as an acylaminoacetamide type compound, is used, but the amount added is as follows: It is 1.0 to 200y per mole of silver halide. 4 equivalents or 2
As equivalent diketomethylene yellow couplers, U.S. Pat. No. 3,277,157, U.S. Pat.
No. 47928, No. 3311476, No. 34081
Compounds described in each specification of No. 94, U.S. Patent No. 287
No. 5057, No. 3265506, No. 340943
No. 9, No. 3551155, No. 3551156,
Compounds described in the specifications of West German Publication No. 1956281 and West German Publication No. 21628, or JP-A-47-2
Compounds described in US Pat. No. 6133 and US Pat. No. 48-66836, as well as US Pat.
No. 148062, No. 3297445, No. 3253
No. 924, No. 3311476, No. 3379529
The "DI
Examples include "R coupler" or "DIR compound".

These couplers can be dispersed in emulsions by the method described in US Pat. No. 2,801,171. Also included are Fisher type couplers in which these couplers are substituted with a water-soluble group such as a sulfo group. In this case, it can be dissolved in an alkaline solution and then mixed into the emulsion. In addition, the silver halide emulsion according to the present invention includes a stabilizer (for example, 4-hydroxy-6-methyl-1.3.C
・7-tetrazaindene, etc.), antifoggants (e.g.,
benzothiazole, 5-mercaptotetrazole, etc.),
Hardening agents (e.g. formaldehyde, glyoxal,
Mucochloric acid, 2,4-dichloro-6-hydroxy-1
・3,5-triazine, aziridine compounds, divinyl sulfones, divinyl ketone, etc.), development accelerators (e.g.
polyalkylene oxides, polyalkylene oxide ethers, esters and amides, thioethers, thiomorpholins, quaternary ammonium compounds, etc.), color couplers as well as color stain inhibitors (e.g. 2,5-di-t-
Hydroquinones such as octylhydroquinone, 2-t-octylhydroquinone, 2-methyl-5-t-octylhydroquinone, etc.), antistatic agents, ultraviolet absorbers,
Photographic additives such as anti-irradiation agents can be included.

The silver halide photographic emulsion according to the invention can be applied to a suitable support, such as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glasses, baryta paper, metals,
Papers coated with polyolefins such as polyethene, polypropylene, etc., synthetic papers etc. may be coated with suitable coating methods such as dip coating,
It is applied by air knife coating, curtain coating, extrusion coating using a hopper, etc.

The silver halide photographic emulsion of the present invention is used in a silver halide photographic light-sensitive material for multilayer color or black and white light-sensitive materials. For example, materials for color positives, materials for color vapors, materials for color negatives, materials for color reversal, materials for plate making (such as lithium film), materials for cathode ray tubes, materials for X-ray recording, materials for diffusion transfer/transfer processes, and color diffusion. Materials for transfer processes, materials for silver dye bleaching, materials for printout recording, materials for forming photo-developable printed images, materials for heat development (
For example, U.S. Patent Nos. 3152904 and 31255
No. 0, No. 3148122, Belgian Patent No. 774
436, etc.). The present invention is characterized by conventional photographic processing (for example, the color development method described in US Pat. In the case of heat-developable light-sensitive materials, there is no contamination due to residual coloring of sensitizing dyes on the materials processed (thermal development process, etc.).Another feature is that the sensitivity in the blue region is greatly increased.

Another feature is that a multilayer color photographic material with good color reproducibility can be obtained. The present invention will be described below with reference to Examples, but these are representative examples of the present invention and, of course, the present invention is not limited thereto.

Example 1 After chemically ripening a chloroiodobromide color positive emulsion containing 0.25 mol % of silver iodide, 19.75 mol % of silver chloride, and 80 mol % of silver bromide, a mulching dye listed in Attached Table 1 was added. 0.1y and 0.15y per mole of silver halide (AgX)
- was added in the form of a methanol solution, and after stirring thoroughly, the adsorption state of the sensitizing dye was stabilized, and then the following yellow coupler [Y] was added as a coupler dispersion composition, mixed and dispersed, and further 4 -Hydroxy-6-methyl-1.3●(●7-tetrazaindene) A blue-sensitive emulsion was prepared by adding a hardener and a coating aid.

Next, after chemically ripening the silver chlorobromide color positive emulsion containing 70 mol% silver bromide and 30 mol% silver chloride, anhydro 5●5''-diphenyl-3●3''-disulfopropyl-9-ethyl- A green-sensitive emulsion was prepared by adding 0.15y of oxacarbocyanine hydroxide per mole of silver halide, and the following magenta coupler [M] and the same stabilizers, hardeners, and coating aids as above were added to this emulsion. A glaucoma emulsion was prepared.

Next, after chemically ripening the silver chloroiodobromide color positive emulsion containing 60 mol% of silver bromide and 40 mol% of silver chloride, anhydro-5.5''-dichloro-3.3''-disulfopropyl-9-ethyl A red-sensitive emulsion was prepared by adding 0.15 y of thiacarbocyanine hydroxide per mole of silver halide, and the following cyan coupler [C] and the same stabilizers and hardeners as above were added to this emulsion to form a red-sensitive emulsion. was prepared.

Each emulsion is coated sequentially on photographic base paper coated on both sides with polyethylene to form a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion, and a thin gelatin film layer and a red-sensitive emulsion layer are placed between each emulsion layer. A multilayer color photographic material was prepared by coating each layer with a gelatin protective layer.

A yellow filter (46
A color positive image was obtained according to the processing steps and recipe described below.

[Color developer]

Benzyl alcohol 12ml Sodium sulfite 2.7f Sodium hydroxide 0.6y Sodium carbonate 20y Potassium bromide
0.4V sodium chloride
1.0V Hydroxylamine Sulfate
2.5y sodium tripolyphosphate
1.0y4-(N-ethyl-N-B-methanesulfonamidoethyl)amino-2-methylaniline sulfate
Add 4f water
Total volume is 1e [Bleach-fix solution] Ethylenediaminetetraacetic acid iron (■) sodium salt
50y70% ammonium thiosulfate aqueous solution 110ml Sodium sulfite
15f Ethylenediaminetetraacetic acid disodium salt 5f Phosphoric acid monoammonium salt
Add 7y of water to make a total volume of 1e [
Stable bath] Sodium citrate 7
Add y potash alum 20y sodium carbonate 3f water
The total amount is 1e.The following [A] is used as a comparative dye for comparison with the sensitizing dye according to the present invention.
~ [E] was used.

Comparative dye [A] Comparative dye [B] Comparative dye [C] Comparative dye [D] Comparative dye [E] Blue light sensitivity, residual color density and Stability over time (results are shown in Table 1).

The relative sensitivity values in the table are for the case without adding sensitization f* (Test N
O. It is expressed as a relative sensitivity of 5, with the sensitivity of 1) being 100. The residual coloring density is expressed by the complementary color density value of the blank area. In addition, the stability over time is expressed as a value obtained when the same test as above is performed after being left for 2 days at a temperature of 50° C. and a relative humidity of 60%. In addition, in order to observe color reproduction with good color balance, the maximum density and tone (r) of the three layers were measured.

The results are shown in Table 2. In this case, the yellow filter used above was removed and light wedge exposure was performed, followed by the same processing. As can be seen from Tables 1 and 2, the multilayer color photographic light-sensitive material using the photographic emulsion of the present invention has well-balanced photographic properties of the three layers and excellent color reproducibility. There is no residual coloration caused by the emulsion, and the storage stability of the emulsion is excellent.

Example 2 Contains % silver iodobromide (7 mol % iodide, 93 mol % silver bromide).

After chemical ripening, the sensitizing dyes listed in Attached Table 3 were added to the emulsion (average grain size: 0.25 microns). This was applied to photographic baryta paper, dried, exposed through a yellow filter, developed at 20° C. for 6 minutes using a developer having the formulation shown below, stopped, fixed, washed with water, and then dried. The relative sensitivity and fog of the obtained images were measured. The results are shown in Table 3.
The display of sensitivity in the table is the test number. 35 is 100,
It is expressed as relative sensitivity when [Developer composition]

Claims (1)

[Scope of Claims] 1. A silver halide photographic emulsion characterized by containing a sensitizing dye represented by the following general formula. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, one of R_1 and R_2 represents a sulfoalkyl group or a carboxyalkyl group, and the other one represents an aralkyl group or a phenoxyalkyl group. However, the aralkyl group and phenoxyalkyl group exclude those substituted with a sulfo group or a carboxy group. Z_1
and Z_2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic nucleus. X represents an acid anion group. n represents an integer of 1 or 2, and when n=1, an inner salt is formed. ]