JPS6024931B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention deals with microscopic spots that occur as a result of foreign matter getting into the photographic emulsion or adhering to the coated photographic emulsion surface during the manufacturing process of photographic light-sensitive materials. This invention relates to a silver halide photographic material that prevents accidents (hereinafter referred to as spots).

When producing silver halide photographic materials, it is common practice to take great care to prevent foreign matter such as dust from entering or adhering to the work place or from the air.

The contamination and adhesion of foreign matter to photographic light-sensitive materials is not desirable in itself, but what is even more troubling is that most of the foreign matter, such as dust, contains metals such as iron and copper. . Therefore, if these foreign substances get mixed into the photographic emulsion or adhere to the surface of the coated photographic emulsion layer, the components in the foreign substances may locally fog or desensitize the photographic emulsion. In order to function, when the obtained photographic material is developed after exposure, black spots or transparent spots containing foreign substances are generated. The degree of spots generated in this way varies greatly depending on the type and composition of the photographic emulsion, the layer structure of the photographic light-sensitive layer, and the nature of the foreign substances causing the problem. The occurrence of this phenomenon is remarkable when the amount of binder is small. In recent silver halide photographic materials, in order to improve properties such as rapid processing characteristics and resolution, there is a tendency to reduce the amount of binder relative to the amount of halogenated synthetic fibers, and as a result, spots are more likely to occur. Prevention has become an important issue. This is particularly true for silver halide photographic materials such as microfilms, which record fine images and later observe them as enlarged images at high magnification, and ultra-high resolution dry plates used to make photomasks used in IC and BI manufacturing. Therefore, prevention of spots caused by foreign matter is an extremely important issue. In order to obtain a silver halide photographic material that prevents the occurrence of spots caused by foreign substances, carbonate, citrate, alcoholate, oxalate, polyphosphate, and tungstate are added to the secondary photographic emulsion*. It is known to add chelating agents such as ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, or their salts.

However, the effects of using these conventionally known substances are not necessarily sufficient, and some of them also exhibit unfavorable effects on the performance of silver halide photographic materials, so that the purpose of preventing spot generation is not sufficiently achieved. At present, there is still nothing that satisfies these requirements. An object of the present invention is to provide a silver halide photographic material that completely prevents the occurrence of spots caused by foreign substances by using two specific types of compounds in combination.

The present inventors conducted extensive research on the effect of preventing the occurrence of spots caused by foreign substances with respect to combinations of various components added to photographic emulsions, and found that at least one of the compounds represented by the general formula 1 below and It has been discovered that a silver halide photographic light-sensitive material that extremely effectively prevents the occurrence of spots can be obtained by coexisting at least one compound represented by the general formula 0 in a silver halide photographic emulsion layer. Ta.

The compound represented by the general formula 1 below is a type of photosensitive dye and is well known as an orthotype color sensitizer for silver halide photographic emulsions. Further, the compound represented by the general formula D described later is also described in Japanese Patent Publication No. 43-4133 and is known as a stabilizer for silver halide photographic materials. However, it was completely unknown to those skilled in the art that the combination of these known substances would very effectively prevent the occurrence of spots caused by foreign substances containing metal. The compound used in the present invention has the general formula 1 (where A and A2 are each a hydrogen atom, a lower alkyl group (e.g., methyl group, ethyl group, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.), a halogen atom ( For example, chlorine atom, bromine atom, etc.), hydroxy group,
Carboxy group or alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), A
3 represents a hydrogen atom or an atomic group necessary to form a benzene ring together with A. A, ton, A2 and A3 cannot form a benzene ring at the same time, although they can be linked together to form a benzene ring.

B. and B2 are hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom, etc.), cyano group, trifluoromethyl group, alkylsulfonyl group, trifluoromethylsulfonyl group, piberidinosulfonyl group, morpholino group, respectively. Sulfonyl group, alkylsulfamoyl group (e.g. methylsulfamoyl group, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkylcarbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, etc.) moyl group, etc.) or alkoxycarbonyl group, R,,R
2 and R3 are each an alkyl group (e.g., methyl group, ethyl group, n-propyl group, etc.), a substituted alkyl group (e.g., an alkyl group substituted with a hydroxy group, acetoxy group, alkoxy group, carboxyl group, sulfoxy group, aryl group, etc.) etc.) or an aryl group. X represents an anion (eg, chloride, furomide, iodide, thiocyanate, sulfonate, perchlorate, p-toluenesulfonate, methylsulfonate, ethylsulfate, etc.). n represents the number 1 or 2, and is 1 when the compound is in the form of an inner salt. ) and general formula D (where R4 is a hydrogen atom or a linear or branched alkyl group (e.g. methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, etc.), and R5 is a hydrogen atom or a hydroxy group. These are two types of compounds. In the present invention, foreign particles can be removed by causing at least one compound represented by the general formula 1 and at least one compound represented by the general formula 0 to coexist in the photographic emulsion layer constituting the photographic light-sensitive material. This prevents spot accidents caused by contamination or adhesion. Therefore,
The present invention can also be applied to the occurrence of spots caused by fine dust adhering to the surface of a plastic film base, which cannot be avoided no matter how careful one takes, for example, due to static electricity charging of the plastic film base. completely prevented by this. In addition, the compound of general formula 1 is a color sensitizer that has a strong sensitizing effect on colored light in the spectrum from green to yellow. If the present invention is applied to the production of super-resolution photographic plates for making photomasks for use in the field of photography, it will be extremely effective in eliminating the occurrence of spots. Representative examples of the compounds represented by formulas 1 and 0 that can be used in the present invention are shown below, but the invention is not limited thereto.

Examples of Compounds of General Formula 1 These compounds represented by general formula 1 are described in the specifications of, for example, Japanese Patent Publication No. 45-127675, Japanese Patent Publication No. 43-1 Makara No. 21, British Patent No. 505979, British Patent No. 812924, etc. It can be easily synthesized according to the method described.

Examples of Compounds of General Formula 0 The above compounds (alkyl esters of gallic acid and protocatechuic acid) can be easily synthesized by known methods.

In order to carry out the present invention, in order to make the compounds represented by the above formula 1 and general formula 0 coexist in the photographic emulsion layer, each compound must be mixed with water, methanol, ethanol, acetone, etc. It may be dissolved in a water-friendly organic solvent such as fluorinated alcohol or a mixture thereof, and then added to the photographic emulsion.

Both compounds exhibit a spot prevention effect when they coexist in the photographic emulsion.
In principle, it is preferable to add both compounds together to the photographic emulsion, but since the compound of general formula 0 is water-soluble and easily moves between layers, it is preferable to add it to the coating solution for forming the intermediate layer or protective layer. However, it is also possible to diffuse the compound into a photographic emulsion layer containing the compound of formula 1 after coating so that they coexist. Both compounds may be added to the photographic emulsion at any time during the photographic emulsion manufacturing process, but it is generally convenient to add them in the adjustment process after chemical ripening. In the case of the compound of general formula 1, the amount added to the photographic emulsion is 10-2 to 10-5 per mole of silver halide.
The molar range is particularly preferably from 10-3 to 10-4 mol, and the compound of general formula 0 is preferably from 1 to 10-3 mol per mol of silver halide. The spot preventing effect due to the synergistic action of the compounds of general formulas 1 and 0 of the present invention is effective regardless of the composition of silver halide in the photographic emulsion used, the grain size of the grains, the crystal habit of the crystals, etc. .

In other words, ha. Regarding the composition of silver genide, the halogenated lines in the photographic emulsion used include silver bromide, silver iodobromide,
Any metal such as silver chloride and silver chlorobromide may be used, and in order to change the emulsion properties, wind group metals such as iridium, rhodium and osmium, or thallium and lead may be added during the formation of silver halide grains or during the physical ripening process. Alternatively, cadmium or the like may be added and contained in the silver halide grains. In addition, it is effective for all ranges of silver halide grain sizes normally used in silver halide photographic light-sensitive materials, and grain crystal morphology such as cubic, octahedral, tabular, or twin crystal. It can be anything. Further, gelatin is generally used as a binder for the photographic emulsion, but derivative gelatin and various water-dropping polymers can also be used. Concessor gelatins include, for example, phenylcarbamyl gelatin, acylated gelatin or phthalated gelatin, or monomers having a polymerizable ethylene group in the molecule, such as acrylic esters, methacrylic acid and methacrylic esters. Examples include those obtained by graft polymerization on gelatin. Various water-soluble polymers include hydrolyzed cellulose acetate, cellulose derivatives such as carboxyalkyl cellulose, polyacrylamide, polypynylpyrrolidone, polyvinyl alcohol, partially saponified polyvinyl acetate, and various other water-soluble polymers. It can also be used. Other useful natural water-soluble polymers include albumin, gum arabic, agar, and alginic acid. The compound of general formula 1 used in the present invention is itself an orthotype color sensitizer as described above, but the present invention further provides a compound of the general formula 1 that can be used in combination with another color sensitizer belonging to merocyanine or carbocyanine. It is also possible to obtain a panchromatic photographic material, and the spot prevention effect of the present invention is not impaired in the slightest even by the combined use of these color sensitizers.

Although almost all known merocyanines and carbocyanines can be used for such purposes, typical examples that are preferably used are specifically illustrated below. Photographic emulsions for use in the present invention can also be chemically sensitized by various known methods.

Namely, sulfur sensitization using thiosulfate, allylisothiocyanate, allylcarbamide, thiourea, cystine, etc. Reduction sensitization using stannous chloride, etc., and gold compounds such as potassium chlorooleate, auric trichloride, potassium auric thiocyanate, 2-aulotiabenzothiazole methyl chloride, ammonium chloroparadate, etc. These include noble metal salt sensitization using palladium compounds, platinum compounds such as potassium chloroplatinate, compounds such as ruthenium, rhodium, and iridium, and chemical sensitization using a combination of these. The photographic emulsion can also contain various additives, if necessary. For example, development accelerators such as thioether compounds, quaternary ammonium salts, and various polyalkylene oxides may be added. It can also be stabilized using various stabilizers. Examples of preferred compounds include 4-hydroxy-5,6-trimethylene-1,3, powder, 7-tetraazaindene, 4-hydroxy-6-menal-1,3, powder, 7-tetraazaindene, 4-hydroxy- 1,3, powder, 7-tetraazaindene and 5-
azaindene compounds such as promoter 6-methyl, 1,3,$,7-tetraazaindene, 1-phenyl-5-
Heterocyclic captan compounds such as captotetrazole and 2-mercaptobenzthiazole, triazole compounds such as triazoles such as 5-nitrobenztriazole, 5-frombenztriazole and 4-methylbenztriazole, 6-nitrobenz Examples include imidazole compounds such as imidazole.
Various additives may be added to the photographic emulsion to which the present invention is applied in order to obtain a uniform coating film or to improve the physical properties of the photographic emulsion layer after finishing.

Various surfactants can be used as spreading agents in order to obtain a uniform coating upon application. Examples of such substances include saponin, polyethylene glycol,
Nonionic surfactants such as alkyl phenoxy polyethylene glycols, alkyl phenoxy polyglycidols, sucrose fatty acid esters, sulfonated succinates such as 2-ethylhexyl sodium sulfosuccinate and amyldecyl sodium sulfosuccinate, dodecylbenzenesulfonic acid anionic surfactants such as alkylated aromatic sulfonates such as soda, sodium triisopropylnaphthalene sulfonate, sodium alkyl polyethylene glycol sulfonate, N-alkyl-N,N-dipolyoxyethylene-N- amphoteric surfactants such as carboxymethyl betaine or nonionic containing fluorinated alkyl groups;
Anionic, cationic, and betaine type surfactants (e.g., manufactured by 3M Corporation in the United States, product code names such as FC-134 and F
C-127 etc.). These surfactants may be used alone or in combination. Hardeners that are primarily used to improve the physical properties of the photographic emulsion layer include, for example, aldehyde and aziridine compounds, isoxazole compounds, epoxy compounds, vinyl sulfone compounds, and acryloyl compounds. , carbodimide compounds, maleimide compounds, acetylene compounds, methanesulfonic acid ester compounds, U.S. Patent No. 3058827, British Patent No. 822061, British Patent No. 1049083, British Patent No. 120
Examples thereof include polymeric compounds and triazine compounds disclosed in Japanese Patent Nos. 2052 and 1230354. Among them, formaldehyde, glyoxal,
Mucochloric acid, 1,3,5-triacryl-1,3,
5-triazine, monomethyloldimethylhydantoin, 1,3-dimethanesulfonylp. /f, dipynylsulfonylethane, 1,2-propylene glycol diglycidyl ether, etc., and these may be used alone or in combination. In addition, in order to further improve the physical properties and dimensional stability of the coating film, a latex emulsion dispersion prepared by emulsion copolymerization of acrylic acid ester 'vinyl ester, etc. with other polymerizable monomers having an ethylene group in the molecule is photographed. It may be added to the emulsion, or glycerin or the like may be added as a plasticizer for the coating film. In order to increase the viscosity of a photographic emulsion containing less binder such as gelatin during coating film formation, sodium polystyrene sulfonate, a copolymer of alkyl vinyl ether and maleic acid, US Pat. No. 3,767,410 and Belgian Patent No. 558,143 are used. It is possible to add compounds such as those disclosed in . Further, in a photographic emulsion containing both compounds of general formulas 1 and 0 of the present invention in coexisting form,
Conventionally known chelating agents such as citrate, tartrate, polyphosphate, and ethylene diamisotetraacetate can also be added in combination. The photographic emulsion containing both the compounds of general formulas 1 and 0 of the present invention, to which various additives as described above have been added as necessary, can be coated on a support suitable for the purpose and dried. The silver halide photographic material of the present invention is obtained.

Supports that are commonly used as supports for photographic materials, such as polymer films such as cellulose acetate, polystyrene and polyethylene terephthalate, paper laminated with polymers, Parata paper, and glass plates, may be used. You can use any * depending on the purpose. The spot prevention effect achieved in the present invention can be obtained in the same way whether the photographic light-sensitive material is subjected to flash exposure or normal exposure.

EXAMPLES Hereinafter, the effects of the present invention will be described in detail using examples, but the embodiments of the present invention are not limited thereto.

In addition, in the following examples, in order to further clarify the effects of the compound of general formula 1 used in the present invention, the following sensitizing dyes were used as comparative sensitizing dyes and compared with the compound of general formula 1. Comparative Sensitizing Dye Example 1 Using a double jet method, a silver dibromide emulsion containing 3 mol % silver iodide with an average grain size of 0.31 was prepared at a concentration of 4 mol % silver halide per mol silver halide during grain formation. ×] Prepared in the presence of 0-7 moles of hexachloroiridate.

After desalting, chemical ripening is carried out by a conventional method, and during this process, sensitization is performed using an appropriate amount of potassium auric thiocyanate and sodium thiosulfate, and the weight ratio of gelatin to silver is 0.95.
It was made into a photographic emulsion. This photographic emulsion was divided into portions, and the compounds of general formulas 1 and 0 and a comparative sensitizing dye were added in individual silk combinations as shown in Table 1 below. At this time, the compound of general formula 1 and the comparative sensitizing dye were used at a concentration of 6×10 per mole of silver halide.
-4 mol, and the compound of general formula 0 was added in an amount of 2 x 10-2 mol per mol of silver halide. To this photographic emulsion, appropriate amounts of 4-hydroxy-6-methyl-1,3,pine,7-tetraazaindene as a stabilizer, mucochloric acid as a hardening agent, and saponin as a spreading agent were added to form a subtracted cellulose triacetate film base. It was coated on top in an amount of 25 parts silver per 100 grounds. After coating, while the photographic emulsion layer is still wet, the sample is divided into three parts, and a small amount of fine powders of iron, copper, and aluminum are uniformly sprinkled on the wet emulsion surface of each sample. Dry. In order to see the occurrence of spots due to metal powder, the dried sample was developed without exposure using Eastman Kodak formulation D-19 imaging solution at 27°C for 2 minutes, and then stopped in the usual manner.
After fixing, washing with water, and drying, spots were observed for each sample. In addition, to measure photographic sensitivity, we used a sample sprinkled with iron powder, and used light from a xenon discharge tube that passed through a blue line filter as a light source.
A second flash exposure was performed, and development was performed under the same conditions as for the spot observation sample, and the photographic sensitivity of the target sample 1 was set as 100, and relative values were displayed. The results are shown in Table 1, and the evaluation of the spot generation status was expressed according to the following criteria. A: No spots occur B: Slight spots occur C: Slightly more spots occur D: Extremely more spots occur Table 1 As is clear from the above table, the compound of general formula 1 and the general formula 0
In Samples 4, 9, and 14 of the present invention, which contain the above compounds coexisting in the photographic emulsion, the occurrence of spots due to the scattering of fine metal powder is significantly prevented.

In contrast, samples containing the compounds of general formula 1 and general formula 0, respectively, had no or very little spot prevention effect. Furthermore, when a comparative sensitizing dye is used, its sensitizing effect is almost the same as that of the compound of general formula 1, but there is no spot effect, and furthermore, even if it coexists with the compound of general formula 0, it has no effect on spot prevention. Also not shown. Example 2 A high-sensitivity silver bromide photographic emulsion containing 5 mol % of silver iodide and having an average grain size of 1 was prepared using a single jet method, and was desalted using a known method to remove unnecessary water-soluble materials. After removing the salts, appropriate amounts of potassium aurelothiocyanate and sodium thiosulfate were added for chemical ripening.

This emulsion was divided, and as shown in Table 2, the compounds of general formulas 1 and 2 used in the present invention or comparative compounds were added in different combinations (the compounds of general formula 1 and the comparative compounds were silver halide 3 x 10-4 mol per mol, and the compound of general formula D has 3 x 10-2 mol per mol of halogenated wire.
Furthermore, as described in Example 1, appropriate amounts of various additives such as stabilizers were added, and this was applied to a subbed cellulose triacetate film base with a coating silver amount of 100. It was applied as silver in an amount of 50 ml. The wet sample of the coated photographic emulsion film was divided into three parts, and fine metal powder was sprinkled on the wet emulsion surface of each sample in the same manner as in Example 1 and dried. Each sample after drying was processed in the same manner as in Example 1, and spots were observed and photographic sensitivity was measured. However, when measuring the photographic sensitivity, the exposure conditions were 1/3 of the light exposure using a KS-7 type sensitometer manufactured by Roku Konishi Photo Industry. The results obtained are shown in Table 2. As is clear from the results in the upper table of Table 2, in samples 18 and 23 of the present invention containing the compound of general formula 1 and the compound of general formula 0 coexisting in the photographic emulsion, the occurrence of Z spots was It can be seen that this is significantly prevented.

As with Example 1, for the other samples as well, the sensitizing effect of the comparative compound is comparable to that of General Formula 1, but even if it is made to coexist with the compound of General Formula 0, it has no effect on spot prevention. Example J Example 3 An example in which the present invention was applied to a low-sensitivity emulsion and color sensitization was performed in combination with other color sensitizing dyes will be described.

The photographic emulsion used was silver chlorobromide fine grain emulsion 2 containing 40 mol % of silver chloride and having an average grain size of 0.25 mounds. Chemical ripening was carried out by adding appropriate amounts of potassium aurelothiocyanate and sodium thiosulfate. This photographic emulsion has a weight ratio of gelatin to silver halide of 0.7, and is a photographic emulsion with a small amount of binder. After chemical ripening, the emulsion is separated and the third
As shown in the table, a compound of general formula 1, a compound of general formula 0,
Comparative sensitizing dyes and general color sensitizing dyes (
m) in various combinations (compounds of general formula 1, comparative sensitizing dyes and dye m at 7 x 10-4 mol per mol of silver halide, compounds of general formula D at 7 x 10-4 mol per mol of silver halide). After adding the stabilizer and other various additives mentioned in Example 1, the amount of silver coated on the photographic polyester film base was 100 cm. The samples were applied to 20 females. As in Example 1, fine powders of iron, copper, and aluminum were sprinkled on the wet photographic emulsion surface of the sample after coating, and dried to obtain a sample for spot generation observation. The sample was treated in the same manner as in Example 1 to measure spot generation and photosensitivity. However, since the photographic emulsion used in this case had low sensitivity, the exposure for measuring sensitivity was carried out for 2 seconds, and the sensitivity value was that of sample No. It was expressed as a value of relative sensitivity with 26 as 100. The results obtained are shown in Table 3. Table 3 As is clear from the results in the above table, no spots were observed in samples 29 and 32 of the present invention, in which the compounds of general formula 1 and general formula 0 were coexisted in the photographic emulsion. Furthermore, sample 33 was added with the aforementioned rainbow compound, which is a general color sensitizing dye, to sample 32.
, 34 and 35, the occurrence of spots is also significantly prevented.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material, characterized in that a compound represented by the general formula I and a compound represented by the general formula II coexist in a silver halide photographic emulsion layer. General formula I ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (Here, A_1 and A_2 are each hydrogen atom, lower alkyl group, alkoxy group, halogen atom, hydroxy group, carboxy group, or alkoxycarbonyl group, A_
3 represents a hydrogen atom or an atomic group necessary to form a benzene ring with A_2, and A_1 and A_2 can also be connected to each other to form a benzene ring, but A_1
and A_2, A_2 and A_3 do not form a benzene ring at the same time. B_1 and B_2 are hydrogen atom, halogen atom, cyano group, trifluoromethyl group, alkylsulfonyl group, trifluoromethylsulfonyl group, piperidinosulfonyl group, morpholinosulfonyl group, alkylsulfonyl group, respectively. Moyl group, alkylcarbamoyl group or alkoxycarbonyl group, R_1, R_2 and R_3 each represent an alkyl group, substituted alkyl group or aryl group, and X represents an anion. n represents the number 1 or 2, and is 1 when the compound is in the form of an inner salt. )
General formula II ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Here, R_4 represents a hydrogen atom or a straight or branched chain alkyl group, and R_5 represents a hydrogen atom or a hydroxy group.)