JPS60239737A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material which has high sensitivity to red light and decreases fogging and color staining by providing at least one emulsion layer contg. silver halide particles sensitized by using at least one kind of the sensitizing dyes expressed by the formula on a substrate. CONSTITUTION:At least one emulsion layer contg. the silver halide particles sensitized by using at least one kind of the sensitizing dyes expressed by the general formula is provided. The heterocyclic ring of the five-membered or six-membered ring expressed by Z1 in the formula is exemplified by, for example, a thiazole ring, quinoline ring, etc. and the heterocyclic ring of the five-membered ring expressed by Z2 is exemplified by, for example, a thiazole ring, naphthoselenazole ring, etc. These rings may have further a substituent. The alkyl groups expressed by R1 and R2 include an alkyl group of 1-4C, substd. alkyl group of 5-8C, etc. The pyridyl group expressed by R3 includes, for example, 2-pyridyl group, 4-pyridyl group and R4 expressed by Y includes an alkyl group of 1-4C, aryl group, etc. R5 expressed by L may the group analogous to the above-mentioned R4. The anion expressed by X is exemplified by, for example, chlorine ion, perchlorate ion, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material, and more specifically, a silver halide photographic material having high sensitivity in the red region and improved adaptability to rapid processing. Regarding materials.

(Prior Art) It is generally known that when a sensitizing dye is added to a photosensitive silver halide emulsion, the sensitive wavelength range of the silver halide emulsion is expanded and the emulsion is optically sensitized.

A large number of compounds have been known as optical sensitizing dyes used for such purposes, such as those described in "The Theory of the Photographic Process" by T.H. James, 4th edition. (1977, Macmillan Publishing,
Cyanine dyes, merocyanine dyes, xanthine dyes, etc. described on pages 194 to 234 are known.

When these sensitizing dyes are normally applied to silver halide emulsions, they must not only simply expand the wavelength range to which the silver halide emulsions are sensitive, but must also satisfy the following conditions.

(1) The spectral sensitization range is appropriate for dye sensitization.

(2) The sensitization efficiency is good and sufficiently high sensitivity can be obtained.

(3) Other types of additives, such as stabilizers, antifoggants,
There should be no adverse interaction with coating aids, coloring agents, etc.

(4) Variation in sensitivity due to temperature changes during exposure is small.

(5) No fogging should occur.

The above conditions have an important meaning especially in the preparation of red-sensitive silver halide emulsions for silver halide color photographic light-sensitive materials.

That is, as sensitizing dyes conventionally used in red-sensitive silver halide emulsions, for example, rhodacyanine dyes and pentamethine dyes are known, but these dyes do not necessarily have sufficient sensitizing efficiency, and Patent No. 2, 4
No. 40,119, No. 2.504.4'68, No. 3
．． Although trinuclear cyanine dyes described in specifications such as No. 335.010 are also known, silver halide photographic materials spectrally sensitized using these trinuclear cyanine dyes suffer from color staining and fogging. This is a problem that is often accompanied by the occurrence of

In addition to the above-mentioned problems, as a result of the rapid progress in recent years in processing systems for silver oxide photographic light-sensitive materials in particular, there has been a strong desire for further improvement in the adaptability of rapid processing to light-sensitive materials.

(Objective of the Invention) Therefore, the object of the present invention is, firstly, to provide high lI for red light.
To provide a silver halide photographic light-sensitive material which has a high temperature and low fogging and color staining,
The object of the present invention is to provide a silver halide photographic material which has high sensitivity and excellent suitability for rapid processing.

(Structure of the Invention) The object of the present invention is to coat at least one emulsion N containing silver halide grains sensitized with at least one sensitizing dye represented by the following general formula on a support. This can be achieved by using a silver halide photographic material having layers.

General formula (0) In the formula, 1 and Z□ are non-gold JI necessary to form a 5-page R1, or a 6-membered heterocycle! represents an atomic group, z2 represents a nonmetallic atomic group necessary to form a 5-membered heterocycle,
R1 and R2 both represent an alkyl group, R3 represents a pyridyl group, Y represents an oxygen atom, a sulfur atom, or a -N- group (wherein R4 represents an alkyl group or an ali group), L represents a methine group or a =C- group (where R5 represents an alkyl group or an aryl group), X represents an anion, m represents an integer of 0 or 1, and p represents O or 1. p represents an integer, and p represents O when the compound represented by the general formula forms an inner salt.

The present invention will be explained in more detail below.

To explain in detail about the sensitizing dye 9 used in the present invention, the 5-membered or 6-membered heterocycle represented by 2□ in the above general formula includes, for example, a thiazole ring, a thiazoline ring, a selenazole ring, and a benzothiazole ring. , benzoselenazole ring, naphthothiazole ring, naphthoselenazole ring, pyridine ring, quinoline ring, etc. Substituents in this case include halogen atoms (for example, chlorine atoms, bromine atoms, etc.), carbon Alkyl group having 1 to 4 atoms (
(e.g. methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, n-propyloxy group, etc.), hydroxy group, aryl group (eg, phenyl group, etc.), and the like.

Examples of the 5-membered heterocycle represented by z2 include a thiazole ring, a thiazoline ring, an oxazole ring, a selenazole ring, a benzoxazole ring, a benzothiazole ring, a benzoxazole ring, a naphthoxazole ring, a naphthothiazole ring, and a naphthoselena ring. Examples include sol rings, which may further have a substituent.

Examples of the substituent in this case include the same groups as the substituent for the heterocycle represented by 2□ above.

Next, as the alkyl group represented by R and R2,
Alkyl groups having 1 to 4 carbon atoms (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 & 2-sulfoethyl group, hoprobyl group, 3-sulfo-1-butyl group, 4-sulfobutyl group, beermethyl group, benzyl group, phenethyl group, p
-sulfophenethyl group, n-propyl group, isopropyl group, n-butyl group, etc.) substituted alkyl groups having 5 to 8 carbon atoms (eg, benzyl group, phenylethyl group, p-sulfophenylethyl group), and the like.

Further, the pyridyl group represented by R3 is, for example, a 2-pyridyl group or a 4-pyridyl group, which may have a substituent. In this case, the substituent is an alkyl group having 1 to 4 carbon atoms. groups (e.g. methyl group, ethyl group, propyl group, etc.), alkoxy groups having 1 to 4 carbon atoms (e.g. methyl, toxy, ethoxy, propoxy groups, etc.), halogen atoms (e.g. chlorine atom, bromine atom), Examples include carbo and xy groups.

4 In addition, as R4 of the -N- group represented by Y in the above general formula,
Alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, 2-
Hydroxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, benzyl group, phenethyl group, ethyl group, propyl group, isopropyl group, etc.) Substitution with 5 to 8 carbon atoms Alkyl groups (e.g. kF! benzyl group, -phenylethyl group, p-sulfophenylethyl group),
Examples include phenyl group, 2-carboxyphenyl group, etc.). R5 In the =C- group represented by L, R5 may be the same group as CR4 above. Furthermore, the anion represented by X is
Examples include chloride ion, bromide ion, iodide ion, p-toluenesulfonate ion, perchlorate ion, and the like.

Typical specific examples of the sensitizing dye represented by the above general formula are described below.

(Exemplary compounds vl) (1) (10) (11) (13) (14) Q(, CkL20G(, CH,OH (15) (16) (18) (19) (20-2H5 (21) (22 ) (24) (26) The trinuclear cyanine sensitizing dye according to the present invention represented by the above general formula is described, for example, by F.M. (
Published by Inter Science Publishers in 1964), U.S. Patent No. g 2,839,403, U.S. Patent No. 2,83
It can be easily synthesized by referring to No. 9.404 and the like.

The method for synthesizing the trinuclear cyanine sensitizing dye according to the present invention will be specifically described below.

Synthesis Example 1゜[Synthesis of 3-2'-pyridylrhodanine] N-2-pyridyldithiocar<<triethylammonium mate (2
7#) was dissolved in 150ml of water, and to this solution was added an aqueous solution of sodium chloroacetate (11,6#) dissolved in 50ml of water at room temperature. - After standing overnight, acidify with acetic acid,
N-2-pyridyldithiocarbamic acid carboxymethy A
-(13,4#, 60%) was obtained. This ester body (1
1.5#) and anhydrous vinegar 1.100% were heated on a steam bath for 1 hour, and then the solvent was distilled off under reduced pressure. The residue was dissolved in isopropanol 70-, left to stand, and the precipitated crystals were collected in a furnace to obtain the desired product 2. SM (21%) was obtained.

Synthesis Example 2 [l-PhenyA-3-2''~Synthesis of pyridyl-2-thiohydantoinj N-phenylaminoethyl acetate (17,91) and N-2
-Methyl pyridyldithiocarbamate (18,37F)
was subjected to a melting reaction at 150°C for 20 minutes.

Ethanol was added to this, and the precipitated crystals were collected to obtain the desired product 9.4# (35%).

Synthesis Example 3 [Synthesis of exemplified sensitizing dye [2]] 2-pensoylmethylene-3-ethylpentthiazole (5,6P), 3-2'-pyridylrhodanine (4,
2#) and benzoic anhydride ('9.0#) at 200°C.
After reacting for 0 minutes, the temperature was returned to room temperature. Methanol 504 was added and stirred, and the wood crystallization t-F was collected. After reacting the thus obtained merocyanine dye '(3,2#) and methyl P,-,)luenesulfonate (3,9#) at 140°C for 1 hour, 3-ethyl-2-methyl-4 , 5-diphenylthiaturium iotide (2,9#), -! -1/-
Add 330ml and 1 ethylamine (2,1#),
Vocal reaction was performed for 1 hour. The temperature was returned to room temperature, the precipitated crystals were collected, and further recrystallized from methanol to obtain the exemplified sensitizing dye (
2) 1.3# (22%) was obtained. The methanol solution of this dye had a λrrtax of 6Q 5 nm.

Synthesis Example 4 [Synthesis of exemplified sensitizing dye [19]] 2-2 hyacetanilide vinylbenzothiazolicum φ iodite <9.0t, 1-722-1-22-pyridyl-2-thiohydantoin ( 5,4t), a mixture of 200d methanol and triethylamine (6,1#)
The reaction mixture was refluxed for a period of time, returned to room temperature, and the precipitated crystals were collected. Merocyanine color 'AC4,6 obtained in this way
t) and P-) methyl luenesulfonate (5,62) at 1
After reacting for 1 hour at 30'C, 3-ethyl-2-methyl-
4,5-diphenylthiazolium° iodite (4,
1#), ethanol 501 and triethylamine (3,0
#) was added, and the mixture was refluxed for 1 hour. Return to room temperature, collect the precipitated crystals, and recrystallize from methanol.
Exemplary sensitizing dye (19) 1.8 t (26%) was obtained. The λmax of the methanol solution of this sensitizing dye is 605n
It was m.

In the present invention, in order to incorporate the sensitizing dye represented by the above general formula into a silver halide emulsion, for example, it is dissolved in water or an organic solvent such as methanol, ethanol, acetone, or fluorinated alcohol, alone or in a mixed solvent.
It may be added at any time during the start of chemical ripening of the silver halide emulsion, during the progress of ripening, after the end of ripening, or just before emulsion. The amount of sensitizing dye added in this case varies depending on the type of rice or emulsion, but it can usually be used in a wide range of 5 to 500 ml per mole of silver halide.
Preferably, the amount is in the range of 10 to 200 m1, but the optimum amount that provides the desired effect within the above range can be arbitrarily selected.

The silver halide emulsion used in the present invention is Mee8"
l”he Tk+eory of the Photo
irafic Process' 3rd edition (1967, published by MaCMi Ilan) pp. 31-43 Oyohi P, () Lafikides, Chimiepho
tographigne' 2nd edition (1957, p.
It can be produced using a neutral method, an acid method, a single jet method, a double jet droplet method, a controlled double jet method, etc., which are described in general specifications such as au1Monte1, pp. 251-308.

The silver halide used in the silver halide emulsion according to the present invention is a conventional silver halide such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Any used in emulsions is included.

The above-mentioned silver halide emulsion is made to contain a Group 8 metal (for example, a water-soluble iridium compound, a water-soluble rhodium compound, a water-soluble palladium compound, etc.) at the time of silver rhodanide crystal formation or physical ripening, so that the emulsion is exposed to high illumination. It can also be achieved by improving short exposure characteristics. In particular, preferred compounds used for the above purpose include trihalogenated iridium salts, tetrahalogenated iridium salts, hexahalogenoiridium (CTI) salts, hexahalogenoiridium (IV) salts, and rhodium halides. Generally, these compounds may be added in an amount of 10-8 to 10-6 mol per mol of silver halide.
In particular, when desensitization or reversal is likely to occur due to the type of metal in the compound used, emulsion preparation method, development method, etc., silO'''8 to I O-' per mole of silver halide.
Preferably, the mol is used before physical ripening.

Hydrophilic colloids advantageously used to prepare the silver halide emulsion according to the present invention include, in addition to gelatin used in ordinary silver halide emulsions, acetylated gelatin,
Gelatin derivatives such as phthalated gelatin, colloidal aluminum, bumin, agar, gum arabic, alginic acid, casein, water-soluble moles derivatives, polyvinyl alcohol, polyvinylhyloritone, or vinyl alcohol,
- Dilucyanoacetate, vinylpyrrolidone, AcryA
-acid, methyl acrylate, vinylimidazole, etc. as copolymers.

These emulsions may also be subjected to chemical sensitization using noble metal sensitizers, sulfur sensitizers, active or inactive selenium sensitizers, reduction sensitizers, polyalkylene oxide sensitizers, etc. It is preferable to use a development accelerator, for example, thioether compounds, quaternary ammonium salts, polyalkylene oxide compounds, etc., and those described in Japanese Patent Publications No. 13822-1982 and No. 11116-1987 are preferred. Rarel is cited as a typical example used. In addition, the emulsion can be stabilized with azoles, azaindenes, mercaptans, etc., and the emulsion can be stabilized with dihydroxyalkanes, cyclohexanediols, acetylene alcohols, or water obtained by emulsion polymerization.
A wetting agent such as a dispersible particulate polymer compound, a fixing agent, a film property improving agent, etc. can be contained.

The silver halide emulsion according to the present invention can contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, gluta-x7A dehyde, etc.), N-methylo-/L-s (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives ( 2,3-dihydroxy-sidioxane, etc.), active vinyl compounds (1,3゜5-triacryloyl-hexahydro-8-) riazine, bis(vinylsulfonyl) methyl ether, etc.), active...rogen compounds (2, 4-dichloro-6-hydroxy-8-) riazine, mucohalokenic acids (mucochloric acid, mucophenoxychloric acid, etc.), inoxazoles, dialdehyde starch, 2-
Chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination; specific examples thereof include U.S. Pat. No. 1,870,354, U.S. Pat. OFk
O,o No. 19, No. 2,726.162, No. 2,
No. 870,013, No. 2,983,611, No. 2
, No. 992,109, No. 3,047,394, No. 3,057,723, No. 3,057,723.

3.103,437, 3,321,313, 3,325,287, 3,362,827,
No. 3,539,644, No. 3,543.292, British Patent No. 676.628, No. 825,544, No. 1,270,578, German Patent No. 872,1
No. 53, No. 1,090,427, Special Publication No. 34-71
No. 33, No. 46-1872, JP-A-53-57257
No. 53-41221, etc.

Additionally, these emulsions contain 4-hydroxy-6-methyl-1,3°3a17- as a stabilizer or anti-capri agent.
Citrazaindene, 3-methylbenzothiazole, 1-
It is possible to contain many heterocyclic compounds, mercury-containing compounds, mercapto compounds, etc., including pheni A-5-mercaptotetrazole. Coating aids such as saponins and sulfosuccinates, fluorescent brighteners such as bistriazinylamine stilbene compounds, supersensitizers such as novolac-type resin condensates of polyhydroxybenzene and formalin, and other color enhancers. Electrodeadractive agent 1. UV absorbers, brighteners,
Halftone dot improver, flame resistant! Various additives for photographic emulsions such as L color formers and toning agents can be contained.

Furthermore, in addition to the sensitizing dye represented by the above general formula, cyanine, merocyanine, composite cyanine, styryl dye, etc. may be used in combination with the halogen/silver oxide emulsion according to the present invention, if necessary. Sensitization may be applied.

The silver halide emulsion prepared above can be applied to a suitable support, such as baryta paper, paper such as polyethylene-coated abrasive, glass plate, cellulose acetate, cellulose nitrate, polystyrene 7'-imum, e.g. It can be applied to polyester films such as polyethylene terephthalate, polycarbonate films, polyamide films, etc. by conventional methods.

In the present invention, exposure to obtain a photographic image is carried out by a conventional method.
That is, any of a variety of known light sources can be used, such as a tungsten electric lamp, a fluorescent lamp, a mercury lamp, a xenon lamp, an arc lamp, a carbon arc lamp, a xenon flash lamp, a halogen lamp, a light emitting diode, a cathode ray tube flying spot, and a discharge tube such as a glow tube. be able to. Exposure time is 1
/ Exposure time from 1000 seconds to 1 second, as well as 1/1
000 seconds.

Shorter exposures, such as exposures of 1/10' to 1/106 seconds with xenon flash lamps, cathode ray tubes, or laser light (He-Ne laser light, argon laser light, etc.) can also be used (1 second). Longer exposures can also be used. Furthermore, the spectral composition of the light used for exposure can be adjusted by color filters as necessary.

The present invention will be explained below with reference to examples, but the present invention is not limited to these examples.

Fruiting example 1 Average particle size prepared by double jet method approximately 0.7
After adding sodium thiosulfate, gold chloride, and ammonium thiocyanate to a polydisperse emulsion of silver iodobromide containing 2 mol% of silver iodide of 0 μm and chemically ripening it under optimal conditions, the emulsion was
The sensitizing dye shown in the first coating was added to each of them in the form of a methanol solution in an amount of 1 mol of silver halide in an amount of bio-5.

Next, appropriate amounts of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene as a stabilizer, saponin 7 as a coating aid, and formalin as a hardening agent were added to each emulsion, and then polyethylene terephthalate was added. A sample was prepared by drying Km cloth on the lid notebook film base.

After applying wedge exposure to the above sample through a red filter (manufactured by Tokyo Shibaura Electric Co., Ltd.) for 1150 seconds,
After developing for 60 seconds at 30° C. with a developer having the composition shown below, it was fixed and washed with water.

(Developer Composition) The density of the obtained silver image was measured to check red light sensitivity and fog.

The results are shown in Table 1 below. Note that the sensitivity is the same for sample 1.
The comparative sensitizing dyes in the table above are illustrated below.

(Comparative sensitizing dyes) (Comparative sensitizing dyes B) (Comparative sensitizing dyes C) As is clear from Table 1 above, samples 1.2 and 1.2 were sensitized using the sensitizing dyes according to the present invention. Sample No. 3 was found to have a superior sensitizing effect and less blur and fog than Comparative Samples 4, 5, and 6, which were all similarly sensitized using comparative dyes.

In fact, the silver iodobromide emulsion prepared and chemically ripened in the same manner as in Example 1 on the downstream side 2° was divided into eight equal parts, and 17 silver halide emulsions were added to each of the sensitizing dyes shown in Table 2 as an external solution of methanol. A sample was prepared, coated, and dried in the same manner as in Example 1 by adding O-' mol of silyl per silyl.

In order to examine the degree of color contamination caused by sensitizing dyes after processing, unexposed photographic materials were used to test XD for automatic processors.
-90 developer (manufactured by Konishiroku Photo Industry Co., Ltd.) at 35℃, 3
Development was carried out for 0 seconds, and after fixing, washing with water, and drying, residual color was visually observed. The residual color property was expressed in four grades from least to least color staining, and is shown in Table 2 below.

Table 2 (degree of color contamination) 1..-.Very clean with only pace density 2..-.Extremely noticeable color contamination Thing 3-1...Things with weak coloring 4
...---... 5.T...Coloration observed.As is clear from Table 2 above, samples 8 to 11 according to the present invention were more susceptible to rapid processing than comparative samples 12, 13, and 14. It can be seen that there is very little color contamination.

(Effect of the invention) A silver halide photographic material having a silver halide emulsion layer optically sensitized with a sensitizing dye represented by the above general formula has high sensitivity to red light and does not cause color staining even during rapid processing. It cannot be caused to occur.

Agent Patent Attorney Yoshiyoshi Nomi Written amendment to parent proceedings July 5, 1980 2 Name of the invention Silver halide photographic light-sensitive material 3 Relationship to the case of the person making the amendment Patent applicant address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Chome 26-2 Name (1
27) Roku Konishi Photo Industry Co., Ltd. 4, Agent Address: 1-6 Sakura-cho, Hino-shi, Tokyo 1-6 Sakura-cho, Hino-shi, Tokyo Column 7 of “Detailed Description of the Invention” of the specification to be amended, Contents of the amendment (1) Page 9 of the specification, line 4 "Benzyl group" to line 5 [ethyl group such as 7-enethyl group] are deleted.

Claims (1)

[Scope of Claims] It is characterized by having at least one emulsion layer containing silver halide grains sensitized using at least one sensitizing dye represented by the following general formula on a support. A silver halide photographic light-sensitive material. General formula [wherein, Zi represents a nonmetallic atom group necessary to form a 5-membered or 6-membered heterocycle, and Z2 represents a nonmetallic atom necessary to form a 5-membered heterocycle 5L represents a methine group or a =to group (wherein R5 represents an alkyl group or an aryl group.) t- represents an anion, m represents an integer of 0 or 1, \p represents 0
or represents an integer of 1, and p represents O when the compound represented by the general formula forms an inner salt. ]