JPH0477305B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material). More specifically, the present invention relates to a method for preserving colloidal silver water compositions used in photosensitive materials. (Prior Art) Colloidal silver used in photosensitive materials is generally produced in an aqueous solvent, and a protective colloid is used to prevent agglomeration of colloidal silver particles. As the protective colloid, gelatin, which is useful for photosensitive materials due to its strong protective colloidal properties, ease of use, and productivity, is widely used. Others, albumin,
Natural polymers such as agar and gum arabic, polymer derivatives such as acylated gelatin, phthalated gelatin, and hydroxyethyl cellulose, or polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, poly-N,N-dimethylacrylamide, A water-soluble synthetic polymer such as polyvinylpyrrolidone is used. The water-soluble polymers (hydrophilic colloids) used in these protective colloids are easily affected by bacteria, yeast, and mold. In particular, the influence of microorganisms is significant on silver halide and water-soluble polymers in which colloidal silver particles are used as protective colloids during production and storage, whether in the gel or sol state. For example, when a protective colloid is putrefied or decomposed by microorganisms, its ability as a protective colloid decreases, colloidal silver particles may aggregate and precipitate, or metabolites of microorganisms may have an adverse photographic effect or cause coloration. There is. It is known that a method of suppressing the growth of microorganisms occurring in a photosensitive material is to include a preservative or an antifungal agent in the photosensitive material. In general, preservatives or antifungal agents for this purpose include, for example, phenol, thymol, trichlorophenol, tetrachlorophenol, pentachlorophenol, cresol,
p-chloro-m-cresol, o-phenylphenol, benzylphenol, 2-benzyl-
4-chlorophenol, chlorophene, dichlorophene, bromochlorophene, 2,2'-dihydroxy-5,5'-dichlorodiphenyl monosulfide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether , 3,4,5-tribromosartylanilide, aromatic hydroxy compounds or salts thereof such as 4-n-hexylresorcinol, or formaldehyde, paraformaldehyde,
Compounds with a carbonyl group such as chloroacetaldehyde, glutaraldehyde, chloracetamide, methylolchloroacetamide, or benzoic acid, monobromoacetate, p-
Carboxylic acids or their esters such as hydroxybenzoic acid esters, sorbic acid, or amines such as hexamethylenetetramine, alkylguanidine, nitromethylbenzylethylenediamine, disulfides such as tetramethylthiuram disulfide, 2-mercaptobenzthiazole, 2 Nitrogen-containing heterocyclic compounds such as -(4-thiazolyl)-benzimidazole, 2-methoxy-carbonylaminobenzimidazole, or organic mercury compounds such as phenylmercuric acetate, phenylmercuric propionate, phenylmercuric oleate, or neomycin Antibiotics such as , kanamycin, polymycin, streptomycin, and flamycin are known, and some of these are also known to be used for photography. However, these substances may not be effective unless added in large quantities to hydrophilic colloids, may be harmful to living organisms, are effective only against certain bacteria, or may be harmful to photographs. In many cases, the bactericidal effect is insufficient due to exposure or interaction with other photographic additives. For example, phenols such as phenol and thymol, which are most often used, do not exhibit a sufficient preservative effect unless they are added in an amount of 2% by weight or more based on the hydrophilic colloid. Furthermore, although phenol has a preservative effect on bacteria, it has little antiseptic and antifungal effect on molds and yeasts, and is highly toxic to living organisms. Furthermore, although aldehydes such as formalin are effective against bacteria, they are less effective against mold, are harmful to living organisms, and tend to fog silver halide photographic materials. Heterocyclic compounds such as benzthiazole may also exhibit photographically deleterious effects, such as desensitizing effects. Although organic mercury compounds are effective against mold, they are less effective against bacteria and are harmful to living organisms. Antibiotics such as neomycin and kanamycin are effective against bacteria, but not against mold and yeast. (Objective of the Invention) The object of the present invention is to provide a preservative method that suppresses the proliferation of microorganisms during the production and storage process of an aqueous colloidal silver composition. The object of the present invention is to provide a preservative method that enables storage over a long period of time. The third purpose is to evaluate the photographic properties of light-sensitive materials (fogging, sensitivity,
graininess, shearness, etc.), physical properties (scratch strength, melting resistance, chargeability, etc.), and coating properties (uniformity of film thickness,
The object of the present invention is to provide a preservative method that does not affect in any way the wettability, etc. (Structure of the Invention) As a result of various studies, the present inventors have found that as a preservative method of the present invention that satisfies these objectives, a compound represented by the following general formula is used in a photographic colloidal silver aqueous composition. A preservative method was constructed in which at least one type of colloidal silver was contained in an amount of 5 x 10 ^-6 to 5 x 10 ^-1 weight % based on the aqueous photographic colloidal silver composition. general formula In the formula, R ₁ represents an alkyl group, a cyclic alkyl group, an aralkyl group, an aryl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group, or an arylsulfonylcarbamoyl group, and R ₂ and R ₃ each represent a hydrogen atom or a halogen Represents an atom, an alkyl group, a cyano group, an alkylthio group, an alkylsulfinyl group, or an alkylsulfonyl group. In R ₁ of the general formula, the alkyl group has 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms. The cyclic alkyl group has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
It is. These alkyl groups, cyclic alkyl groups, aralkyl groups and aryl groups may have a substituent, and the substituents include halogen atom, nitro, cyano, thiocyano, aryl, alkoxy, aryloxy, carboxy, sulfoxy,
Alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl,
Sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamide, heterocyclic group, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl Nyl, arylsulfinyl, alkylamino, dialkylamino, anilino, N-alkylanilino, N-arylanilino, N-acylamino, hydroxy, and mercapto groups. In R ₂ and R ₃ of the general formula, the alkyl group has 1 to 18 carbon atoms, more preferably 1 to 9 carbon atoms. The alkyl group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a sulfone group, an aryl group, and a hydroxy group. Typical specific examples of the compound represented by the above general formula (hereinafter referred to as the compound of the present invention) are shown below, but the compound of the present invention is not limited thereto. [Exemplary compounds] 2-(N-methylcarbamoyl)-3-isothiazolone, 5-methyl-2-(N-methylcarbamoyl)-3-isothiazolone, 2-(N-methylthiocarbamoyl)-3-isothiazolone, 4-bromo -5-Methyl-2-(N-methylcarbamoyl)-3-isothiazolone, 4-cyano-5-methylthio-2-(N-methylcarbamoyl)-3-
Isothiazolone, 4-cyano-5-methylsulfinyl-2-(N-methylcarbamoyl)-3-isothiazolone, 4-cyano-5-,methylsulfonyl-2-(N-methylcarbamoyl)-3-isothiazolone, 2 -(N-n-butylcarbamoyl)
-3-isothiazolone, 2-(N-t-octylcarbamoyl)-3-isothiazolone, 5-methyl-2-(N-phenylcarbamoyl)-3-isothiazolone, 4-cyano-5-methylthio-2-
(N-phenylcarbamoyl)-3-isothiazolone, 4-bromo-5-methyl-2-(N-3-chlorophenylcarbamoyl)-3-isothiazolone, 5-bromomethyl-2-(N-3-chlorophenylcarbamoyl) )-3-isothiazolone, 5
-Methyl-2-(N-3-chlorophenylcarbamoyl)-3-isothiazolone, 4-cyano-5
-Methylthio-2-(N-3-chlorophenylcarbamoyl)-3-isothiazolone, 2-(N-3
-chlorophenylcarbamoyl)-3-isothiazolone, 5-methyl-2-(N-2-chlorophenylcarbamoyl)-3-isothiazolone, 5-
Bromomethyl-2-(N-2-chlorophenylcarbamoyl)-3-isothiazolone, 4-bromo-5-methyl-2-(N-3,4-dichlorophenylcarbamoyl)-3-isothiazolone, 5-
Methyl-2-(N-3,4-dichlorophenylcarbamoyl)-3-isothiazolone, 4-cyano-5-methylthio-2-(N-3,4-dichlorophenylcarbamoyl)-3-isothiazolone,
5-methyl-2-(N-4-tosylcarbamoyl)
-3-isothiazolone, 4-cyano-5-methylthio-2-(N-4-tosylcarbamoyl)-3-
Isothiazolone, 4-bromo-5-methyl-2-
(N-4-tosylcarbamoyl)-3-isothiazolone, 2-(N-n-propylcarbamoyl)-3
-isothiazolone, 2-(N-ethylcarbamoyl)-3-isothiazolone, 2-(N-i-propylcarbamoyl)-3-isothiazolone, 4-bromo-2-(N-methylcarbamoyl)-3-isothiazolone, 2- (N-4-methoxyphenylcarbamoyl)-3-isothiazolone, 2-(N-2
-methoxyphenylcarbamoyl)-3-isothiazolone, 2-(N-3-nitrophenylcarbamoyl)-3-isothiazolone, 2-(N-3,4
-dichlorophenylcarbamoyl)-3-isothiazolone, 2-(N-n-dodecylcarbamoyl)
-3-isothiazolone, 2-(N-2,5-dichlorophenylcarbamoyl)-3-isothiazolone, 2-(N-carboethoxymethylcarbamoyl)-3-isothiazolone, 2-(N-4-nitrophenylcarbamoyl) )-3-isothiazolone,
5-Methyl-2-(N-ethylcarbamoyl)-3
-isothiazolone, 5-methyl-2-(N-ethylthiocarbamoyl)-3-isothiazolone, 5
-chloro-2-(N-ethylcarbamoyl)-3-
Isothiazolone, 2-n-propyl-3-isothiazolone, 2-t-butyl-3-isothiazolone, 2-n-butyl-3-isothiazolone, 2-
Cyclohexyl-3-isothiazolone, 2-t-
Octyl-3-isothiazolone, 2-benzyloxy-3-isothiazolone, 5-chloro-2-methyl-3-isothiazolone, 5-chloro-2-benzyl-3-isothiazolone, 4,5-dichloro-2-methyl-3 -isothiazolone, 2,4-dimethyl-3-isothiazolone, 4-methyl-2-
(3,4-dichlorophenyl)-3-isothiazolone, 2-(3,4-dichlorophenyl)-3-isothiazolone, 4,5-dichloro-2-benzyl-
3-isothiazolone, 4-bromo-5-chloro-
2-Methyl-3-isothiazolone, 4-bromo-
2-Methyl-3-isothiazolone, 2-hydroxymethyl-3-isothiazolone, 2-(β-diethylaminoethyl)-3-isothiazolone, 2-
n-propyl-3-isothiazolone hydrochloride, 5-
Chloro-2-methyl-3-isothiazolone hydrochloride, 2-ethyl-3-isothiazolone hydrochloride, 2
-Methyl-3-isothiazolone hydrochloride, 2-benzyl-3-isothiazolone hydrochloride, 2-n-dodecyl-3-isothiazolone, 2-n-tetradecyl-3-isothiazolone, 2-(4-chlorobenzyl)-3- Isothiazolone, 2-(2-chlorobenzyl)-3-isothiazolone, 2-(2-chlorobenzyl)-3-isothiazolone, 2-(2,4-
dichlorobenzyl)-3-isothiazolone, 2-
(3,4-dichlorobenzyl)-3-isothiazolone, 2-(4-methoxybenzyl)-3-isothiazolone, 2-(4-methylbenzyl)-3-isothiazolone, 2-(2-ethoxyhexyl)-3- Isothiazolone, 2-(2-phenylethyl)-3-
Isothiazolone, 2-(2-phenylethyl)-4
-chloro-3-isothiazolone, 2-(1-phenylethyl)-3-isothiazolone, 2-n-decyl-3-isothiazolone, 2-n-octyl-
3-isothiazolone, 2-t-octyl-4-chloro-3-isothiazolone, 2-t-octyl-
4-bromo-3-isothiazolone, 2-n-nonyl-3-isothiazolone, 2-n-octyl-5
-chloro-3-isothiazolone, 2-(4-nitrophenyl)-3-isothiazolone, 2-(4-carboethoxyphenyl)-3-isothiazolone,
5-chloro-2-methyl-3-isothiazolone.
Monochloroacetate, 4,5-dichloro-2-methyl-3-isothiazolone monochloroacetate, 2
-Ethyl-3-isothiazolone monochloroacetate, 2-n-propyl-3-isothiazolone monochloroacetate, 2-benzyl-3-isothiazolone monochloroacetate. These exemplified compounds are covered by French Patent No. 1555416.
Synthesis methods and examples of application to other fields are described in the above issues, but examples of sterilization and prevention of hydrophilic colloids for photosensitive materials are not mentioned or even suggested at all. The conditions that must be met as a sterilization and antifungal agent for hydrophilic colloids for photosensitive materials are [1]
It does not interact with photographic additives, [2] It has a large bactericidal and antifungal effect in small amounts, [3] It does not affect photographic performance such as desensitization, fogging, graininess, sharpness, etc., [4] Development It is desired that there be no effect on processing performance such as silvering properties, desilvering properties, and recoloring properties; [5] there should be no effect on the environmental ecosystem; [6] there should be no adverse effects on the human body. The compound of the present invention satisfies all of these requirements. The compound of the present invention is contained in an amount of 5 x 10 ^-6 to 5 x 10 ^-1 % by weight based on the aqueous colloidal silver composition. The compound of the present invention can be dissolved or emulsified in water or an organic solvent such as methanol, ethanol, isopropanol, acetone, or ethylene glycol that does not adversely affect photographic performance or physical properties, or can be dissolved or emulsified in a high-boiling point solvent or a low-boiling point solvent. After dissolving it in a solvent or a mixed solvent of both, it may be emulsified and dispersed in the presence of a surfactant and added to an aqueous colloidal silver composition (hereinafter, the liquid form is referred to as an aqueous dispersion), and it may be gelled. The aqueous composition may be applied to the surface, or the gelled colloidal silver aqueous composition may be immersed in a disinfectant solution or emulsified dispersion. The compound of the present invention may be added during or after the production of the colloidal silver aqueous composition. The colloidal silver aqueous dispersion used in the present invention is one in which silver particles of 0.5 microns or less are dispersed in an aqueous solvent, exhibits a color such as yellow or black, and is generally used for filters or for preventing halation. Various methods have been proposed for producing colloidal silver, for example, "Colloidal Silver" by Weiser.
Elements “Wiley & Sons (New York
1933), German Patent No. 1096193, US Patent No. 2688601
The methods described in this issue can be usefully used. The colloidal silver aqueous dispersion in the present invention is prevented from agglomerating by the protective colloid. Gelatin is usually used as a protective colloid, but other natural polymers such as albumin, agar, gum arabic, etc.
Polymer derivatives such as acylated gelatin and phthalated gelatin, and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, and polyacrylic acid are used. When the colloidal silver according to the present invention is used in an antihalation layer or a filter layer, the colloidal silver aqueous dispersion is further supplemented with a binder and coated. The content of colloidal silver is usually expressed in milligrams per 100 cm ² of surface area of the support of the photographic element, and is usually applied in a range of 1 to 100 mg. The colloidal silver of the present invention can be used together with a light-sensitive silver halide photographic emulsion, and the light-sensitive silver halide agent can be prepared by a known method. When the colloidal silver of this invention is used in color photography, it can be used with internal color development type emulsions containing dye-forming couplers.
Dye-forming couplers can also be used with external color development type emulsions in which the dye-forming couplers are supplied from a developer solution. Such color photographic development methods typically use a bleaching process, such as oxidative bleaching, to remove the silver image. In this bleaching process, colloidal silver is also bleached and becomes transparent. These colloidal silvers can also be usefully used in light-sensitive materials for multilayer color diffusion transfer. (Example) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the Examples. Example 1 Compounds (1) to 1 of the present invention were added to antihalation black colloidal silver dispersion 1 prepared by a conventional method.
(27) and comparative compounds [X], [Y], [Y ₁ ], respectively.
Ten
mg, prepare samples 1 to 6 shown in Table 1, inoculate each sample with one strain of Pseudomonas layer,
After being left at 25°C for one week, the number of bacteria, viscosity, and aggregation state of colloidal silver were examined.

【table】

[Color developer composition]

4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1 and adjust the pH to 10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to bring the solution to 1 and adjust the pH to 6.0. [Fixer composition] Ammonium thiosulfate 50% aqueous solution 162ml Anhydrous sodium sulfite 12.4g Add water to bring the solution to 1 and adjust the pH to 6.5. [Stable bath composition] Formalin 37% aqueous solution 5.0ml Konidax [manufactured by Konishiroku Photo Industry Co., Ltd. 7.5ml Add water to make 1. Green light sensitometry was performed on each developed sample. The growth status of mold and the results of sensitometry are shown in Table 2. Regarding the evaluation of the mold growth status, those with very good growth of mold hyphae and spores are classified as 1st grade, those with only a slight amount of mold hyphae observed as 2nd grade, and those with no mold hyphae appearing at all. The item was classified as 3rd class. Also, the sensitivity is that of sample No. 7.
The relative sensitivity is expressed as 100.

【table】

[Table] (Note) The yellow and black colloidal silver solutions expressed as a pair with the same sample number gave exactly the same results.
As is clear from Table 2, the compounds of the present invention have no effect on photographic performance and completely suppress the growth of bacteria and mold. On the other hand, no bactericide added (sample no.
8) and addition of a small amount of comparative compound (sample No. 15,
16) had decreased sensitivity and increased fog. In addition, the compound of the present invention is 1000% of the comparative compound (X).
It had more than double the sterilizing and anti-mold effect. Compound of the present invention (28) 2methyl-5-chloro-3-isothiazolone hydrochloride (Effects of the Invention) The objects of the present invention are preferably satisfied, and the productivity of photosensitive materials is improved by enabling long-term storage of aqueous compositions, reducing loss of coating compositions, and easing environmental conditions at manufacturing sites. Significantly improved. Furthermore, there was a contribution to be made in terms of quality assurance for users.

Claims (1)

[Scope of Claims] 1. At least one compound represented by the following general formula is added to an aqueous photographic colloidal silver composition in an amount of 5×10 ^-6 to 5× with respect to the aqueous photographic colloidal silver composition.
A method for preserving an aqueous photographic colloidal silver composition, characterized in that it contains 10 ^-1 % by weight. general formula [In the formula, R ₁ is an alkyl group, a cyclic alkyl group,
Represents an aralkyl group, an aryl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group, or an arylsulfonylcarbamoyl group, and R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, a cyano group, an alkylthio group, or an alkylsulfonylcarbamoyl group. Represents a finyl group or an alkylsulfonyl group. ]