JPH0664314B2 - Preservative and method for preserving photographic colloidal composition - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a preservative and a preservative method for a photographic colloid composition used in a silver halide photographic light-sensitive material (hereinafter simply referred to as "light-sensitive material"). Is.

2. Description of the Related Art Photosensitive materials generally include at least one photosensitive emulsion layer and, if necessary, constituent layers such as an undercoat layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and a backing layer. It is formed by laminating and coating on a support.

These constituent layers include a silver halide in a hydrophilic binder such as gelatin in addition to silver halide, depending on the purpose of use of the light-sensitive material.
It contains couplers, masking couplers, stabilizers, inhibitors, filter dyes, antihalation dyes, sensitizing dyes, colloidal silver, ultraviolet absorbers, antioxidants, matting agents, surfactants and the like.

These additives are usually dissolved or dispersed in an aqueous solvent such as water, alcohol or a mixture thereof, or dissolved in a water-insoluble solvent having a high boiling point or dispersed as fine oil droplets, and these are hydrophilic. It is added to the colloid to form a coating composition for constituent layers.

Here, the hydrophilic colloid is a polymer substance used to prevent aggregation of silver halide, colloidal silver, and other additives, and gelatin is most widely used. In addition, albumin, agar, gum arabic, etc. Natural substances such as
Polymerized derivatives such as acylated gelatin, phthalated gelatin, hydroxyethyl cellulose, polyvinyl alcohol, partially saponified polyvinyl acetate,
Water-soluble polymers such as polyacrylamide, poly-N, N-dimethylacrylamide, and polyvinylpyrrolidone are used.

Therefore, the additive solution for the constituent layer or the coating composition for the constituent layer is easily proliferated by microorganisms such as bacteria and mold during storage, and is deteriorated or spoiled when stored for a long time, resulting in a decrease in viscosity of the coating composition. In addition, the physical strength of the surface coating of the light-sensitive material is lowered, and metabolites of proliferated microorganisms adversely affect the photographic performance of the light-sensitive material, resulting in a serious defect.

It is known to add a bactericidal agent or an antifungal agent to the coating composition in order to prevent the occurrence of such defects caused by microorganisms.

Generally, as fungicides or antifungal agents, for example, phenol, thymol, trichlorophenol, cresol, p
-Chloro-m-cresol, o-phenylphenol,
Chlorophen, 3,4,5-tribromosalicylanilide,
Aromatic phenols such as 4-n-hexylresorcin; Compounds having a carbonyl group such as formaldehyde, paraformaldehyde, glutaraldehyde, and methylolchloraldehyde; Carboxylic acids such as benzoic acid, p-oxybenzoic acid esters and sorbic acid; Nitrogen-containing heterocyclic compounds such as 2-mercaptobenzothiazole and 2- (4-thiazolyl) benzimidazole; Mercury compounds such as phenylmercury and mercury phenylpropionate; Antibiotics such as neomycin and kanamycin; Others are known. Some of them are also known to be used in photographic colloidal compositions.

However, the conventional ones are not satisfactory because they are not effective unless they are added in a large amount to the hydrophilic colloid, are harmful to the living body, or are photographically harmful.

For example, phenols do not exhibit a sufficient antiseptic effect unless added in a large proportion of 2% or more of the hydrophilic colloid.

When formaldehyde or the like is used, the light-sensitive material tends to cause fog.

Benzthiazoles and the like easily give a desensitizing effect to a light-sensitive material.

Mercury compounds are harmful to living organisms and their use should be avoided.

Further, the compounds described in Japanese Patent Application No. 58-227522 may adversely affect the photographic performance of certain photosensitive materials, and neomycin described in Japanese Patent Publication No. 42-14081 is expensive. is there.

As described above, none of the conventional bactericides or antibacterial agents has practically satisfactory properties when added to the photographic colloid composition as a preservative.

II Object of the Invention A first object of the present invention is to effectively protect an additive solution or a coating composition solution for a constituent layer of a light-sensitive material, that is, a photographic colloid composition, from microorganisms and improve its storage stability. Moreover, it is an object of the present invention to provide a preservative and a preservative method for a photographic colloid composition, which can be used in a small amount.

A second object of the present invention is to provide a preservative and a preservative method for a photographic colloid composition, which does not adversely affect photographic performance such as sensitivity, fog and storability of a light-sensitive material.

Other objects of the present invention will be apparent from the following description.

III Specific Structure of the Invention As a result of various investigations, the present inventors have found that the compound represented by the following general formula is effective as a preservative for a photographic colloid composition, and the compound is It has been found that the object of the present invention can be achieved by incorporating at least one of the above in a photographic colloid composition.

General formula (However, R ₁ and R ₂ are different or identical to each other and represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms or a hydroxymethyl group, and R ₃ is a hydrogen atom, 1 to 1 carbon atoms. 5 represents a lower alkyl group.) In the above general formula, the lower alkyl group for R ₁ , R ₂ or R ₃ is particularly preferably one having 1 or 2 carbon atoms.

The preservative of the present invention containing the compound represented by the above general formula as an active ingredient is particularly a coating composition comprising a matting agent dispersion, a coupler dispersion, a silver halide emulsion, an ultraviolet absorbing dispersion, or a mixture thereof. Is especially useful for preservation of

The amount of the preservative used is preferably 0.001 to 0.05% by weight based on the aqueous solution which is the colloidal composition for photography and other solutions to be added. However, it goes without saying that this range may be increased or decreased depending on the type of light-sensitive material, the type of aqueous solution, the storage state, and the like.

The preservative of the present invention is water or methanol, ethanol,
It may be added as a solution dissolved in a solvent such as isopropanol, acetone, ethylene glycol or a mixed solvent thereof, or after being dissolved in a high boiling point solvent or a low boiling point solvent, emulsified and dispersed using a surfactant and added. May be.

Specific examples of the compound represented by the above general formula are shown below. Note that bp. Is the value at 10 mmHg.

These compounds can be synthesized with reference to the following documents, and some of them are commercially available from Sanai Petroleum Co., Ltd.

(1) E. Schmidt, R. Wilkendorf, Berichte der Deutchen Ch
emischen Geselschaft, 52, 392 (1919) (2) BM Vanderbilt, HB Haas, Ind. Eng. Chem., 32, 3
4 (1940) (3) IM Gorsky, SP Makarow, Berichte der Deutche
n Chemischen Geselschaft, 67, 996 (1934) The time of addition of the preservative of the present invention is arbitrarily selected depending on the time of exhibiting the preservative effect.

The photographic colloid composition to which the preservative of the present invention is added is a solution of a hydrophilic colloid in an aqueous solvent. The hydrophilic colloid and aqueous solvent used are as described above.

The additives contained in the photographic colloid composition targeted by the present invention may be any of the usual photographic additives. A suitable example is shown below.

i) Coupler: α- (4-carboxyphenoxy) -α-pivalyl-2
-Chloro-5- [γ-2,4-di-tert-amylphenoxy) butyramide] acetanilide, α-pivalyl-2-chloro-5- [γ-2,4-di-tert
-Amylphenoxy) butylamido] acetanilide, α-benzoyl-2-chloro-5- [α-dodecyloxycarbonyl) ethoxycarbonyl] acetanilide, α- (4-carboxyphenoxy) -α-pivalyl-2
-Chloro-5- [α-3-pentadecylphenoxy) butyramide] acetanilide, 1- (2,4,6-trichlorophenyl) -3- [3- (2,4
-Di-tert-amylphenoxyacetamido) benzamido] -5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3- (3-dodecylsuccinimidobenzamide) -5-pyrazolone, 4,4'- Methylenebis {1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-tert-aluminphenoxyacetamido) benzamide] -5-pyrazolone}, 1- (2,4,6 -Trichlorophenyl) -3- (2-chloro-5-octadecylsuccinimidoanilino) -5-
Pyrazolone, 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-tetradecanamidoanilino) -5-pyrazolone, 1-hydroxy-N- [8- (2,4-di- tert-amylphenoxy) butyl] -2-naphthamide, 2,4-dichloro-3-butyl-6- (2,4-di-tert-amylphenoxyacetamido) phenol, 1-hydroxy-4- (4-nitrophenyl) Carbamoyl) oxy-N- [8- (2,4-di-tert-amylphenoxy) butyl] -2-naphthamide, and the like.

ii) High boiling point solvent: dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phthalate, N, N-
Diethyldodecane amide, di-natoxyethyl phthalate, etc.

iii) Noble metal sensitizers: chloroauric acid, potassium chloroaurite, potassium aurithiocyanate, ammonium chloroparadate, sodium chloroiridate, and others.

iv) Sulfur sensitizer: active gelatin, sodium thiosulfate, ammonium thiosulfate, N-allyl rhodamine, and others.

v) Reduction sensitizer: stannous chloride, tetraethylenetriamine, iminoaminomethanesulfinic acid, and others.

vi) Sensitizing dye: Anhydro-9-ethyl-bis (3-sulfopropyl-)
5-chloro) oxacarbocyanine hydroxide, anhydro-9-ethyl-bis (3-sulfobutyl-5)
-Chloro) thiacarbocyanine hydroxide, 3-sulfobutyl-3'-ethylthiacyanine sodium salt, and the like.

vii) Stabilizer: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, benzothiazole, etc.

viii) Matting agent: silica, magnesium phosphate, titanium oxide, polymethylmethacrylate, polystyrene, starch, cellulose acetate propionate, and others.

ix) Surfactant: saponin, polyoxyethylene nonyl phenyl ether sodium sulfate, polyoxyethylene lauryl ether sodium sulfate, polyexethylene nonyl phenyl ether,
Polyoxyethylene-polyglycidal block copolymer, etc.

x) High-molecular hydrophilic colloid: a copolymer of methyl methacrylate, n-butyl acrylate, butadiene, styrene, vinyl acetate, vinyl chloride, etc., and others.

As the silver halide, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or the like may be used.

IV. Specific Actions and Effects of the Invention According to the present invention, an antiseptic composition containing, as an active ingredient, one or more compounds represented by the above general formulas 1 to 3 in a photographic colloid composition used for coating a light-sensitive material. Because the agent is added,
Due to the antiseptic action of the compound, the photographic colloid composition can be effectively protected from microorganisms and excellent storage stability can be obtained.

Moreover, the preservative is sufficient because the amount used is small.

Moreover, it does not adversely affect the photographic performance of the light-sensitive material, such as sensitivity, fog and storability.

Furthermore, since the preservative is inexpensive, it does not increase the cost of the light-sensitive material unlike antibiotics.

Therefore, it is possible to significantly reduce equipment burdens such as storage facilities, restrictions on production plans, malfunctions in photographic performance and physical properties, etc.
It is possible to obtain extremely large effects such as improvement in productivity of photosensitive materials and improvement in quality reliability.

V Specific Examples of the Invention Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example 1 To an aqueous dispersion 1 of a matting agent made of polymethylmethacrylate having an average particle size of 3 μm, 25 mg of each of the compound (1) and the compound (3) described above according to the present invention as a preservative was added, and a total of 2 A seed matting agent dispersion was prepared. These are designated as Sample 1 and Sample 2.

Further, a comparative matting agent dispersion was prepared in the same manner except that 25 mg of phenol was added as a preservative for comparison. This is designated as Comparative Sample 1.

Furthermore, Pseudomo was added to each of these three types of matting agent dispersions.
A storage test was carried out by inoculating one nas genus strain and leaving it at a temperature of 25 ° C. for one week. The number of bacteria after the storage period was measured, and the dispersed state of the matting agent was also observed. Further, a matting agent dispersion liquid to which no preservative is added is used as a control, and a case where the matting agent dispersion liquid is used as it is without storage is referred to as a control sample 1, and a case where a similar storage test is performed is referred to as a control sample 2. The results are shown in Table 1.

Further, a high-sensitivity X-ray photosensitive material was produced by the following method using the total 5 kinds of matting agent dispersions as described above.

That is, a potassium bromide solution containing 2.5 mol% of potassium iodide and an ammoniacal silver nitrate solution were added to a gelatin aqueous solution by a double jet method while gradually increasing the flow rate to obtain an iodobromide having an average particle size of 1.05 μm. A silver octahedron monodisperse emulsion was obtained. Further, an ammoniacal silver nitrate solution and a potassium bromide solution were added by the double jet method to form a pure silver bromide shell. During this period, pAg is maintained at 10.0 and pH is 9.0 to 8.0.
Gradually lowered. This emulsion was a regular octahedral monodisperse emulsion having an average grain size of 1.25 μm.

Then, after desalting, the emulsion was subjected to gold sensitization and sulfur sensitization, and then stabilized by adding 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, and further a spreading agent, A general photographic additive such as a hardener was added to obtain a high-sensitivity X-ray silver iodobromide emulsion.

On the other hand, each of the above-mentioned 5 types of matting agent dispersions was used to prepare a coating liquid for protective layer having the following composition.

Gelatin 50 g Sodium diisooctyl sulfosuccinate (1% aqueous solution) 30 ml Antistatic agent 2 g Matting agent dispersion 30 g Water amount to be 1 and the above high sensitivity on blue dyed and subbed polyethylene terephthalate film base The X-ray silver iodobromide emulsion and the coating solution for the protective layer were simultaneously coated and dried to prepare a high-sensitivity X-ray photographic material having a silver content of 30 mg / 100 cm ² .

Sensitometry was performed under the following conditions using each of these X-ray photosensitive materials as a sample.

The exposure is carried out by holding the sample sandwiched between two optical wedges on one side of the transparent support, and simultaneously exposing it with a light source with a color temperature of 5,400 ° K from both sides at the same amount of light for 1/10 seconds. The process was carried out using a roller-conveying type automatic processor according to steps a to d under the following conditions. Process Treatment temperature Treatment time Development 35 ° C 25 seconds Fixing 34 ° C 25 seconds Washing 33 ° C 25 seconds Drying 45 ° C 15 seconds The developing solution used here is a developing solution of the following composition, and the fixing solution is an acid hard solution. Membrane fixer "Sakura XF" (made by Konishi Rokusha Kogyo)
Was used.

[Developer composition]

Potassium sulfite 55.0g Hydroquinone 25.0g 1-phenyl-3-pyrazolidone 1.2g Boric acid 10.0g Potassium hydroxide 21.0g Triethylene glycol 17.5g 5-Methylbenztriazole 0.04g 5-Nitrobenzimidazole 0.11g 1-Phenyl-5- Mercaptotetrazole 0.015 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Water amount to be 1 Table 1 shows the results. Sensitivity is 100 times that of control sample 1.
The relative sensitivity is shown below.

From the results shown in Table 1, in Samples 1 and 2 according to the present invention, the photographic performance was not adversely affected, the activity of bacteria was effectively suppressed, and the matting agent was used even after the storage period of 1 week. It is clear that no aggregation has occurred.

Example 2 To a gelatin aqueous dispersion 1 containing polymer particles of polyethyl acrylate prepared by a usual method, 100 mg of each of the above-mentioned compound (1) and compound (3) according to the present invention was added as a preservative, A total of two gelatin dispersions were prepared. These are designated as Sample 3 and Sample 4.

Also, as a comparative preservative, a comparative matting agent dispersion was prepared in the same manner except that 100 mg of each of compound X and phenol represented by the following structural formula described in Japanese Patent Application No. 58-227552 as compound example 1 was added. Was prepared. These are designated as Comparative Sample 2 and Comparative Sample 3.

Compound X Furthermore, Acinetob was added to each of these four gelatin dispersions.
A storage test was performed in which one strain of the genus acten was inoculated and left at 25 ° C for one month, the number of bacteria after the storage period was measured, and the dispersed state was also observed. Further, a gelatin dispersion liquid containing no preservative is used as a control, and a case where it is used as it is without storage is set as control sample 3, and a case where the same storage test is performed is set as control sample 4. Result is second
As shown in the table.

Further, a lithographic light-sensitive material was prepared by the following method using a total of 6 types of gelatin dispersions as described above.

That is, 5 ml of each of the above gelatin dispersions was added to 100 ml of a squirrel-type silver halide emulsion to prepare an emulsion coating solution, which was coated on a polyethylene terephthalate support by a conventional method and dried to obtain 6 types of lith-type photosensitive materials. Were manufactured, and each of them was subjected to sensitometry and halftone dot evaluation.

The sensitometry was carried out by exposing with a KS-1 type sensitometer and then using the following developer at a temperature of 27 ° C and a processing time of 1 minute 40.
After developing under the condition of second, fixing and washing treatment were performed.

[Developer composition]

Anhydrous sodium sulfite 3g Formaldehyde-sodium sulfite adduct 50g Boric acid 7g Potassium bromide 2.5g Anhydrous sodium carbonate (monohydrate) 80g Water The total amount is 1. Table 2 shows the results. In the halftone dot evaluation, sharp and small fringes around the halftone dots were classified as grade 5, and those with very large fringes were classified as grade 1, and the intervals between them were classified into grade 4, grade 3, and grade 2. The sensitivity is shown as a relative sensitivity with the sensitivity of Control Sample 3 being 100.

From the results shown in Table 2, in the case of Samples 3 and 4 according to the present invention, there is no adverse effect on the photographic performance of the obtained light-sensitive material, and a strong inhibitory effect on the growth of bacteria is obtained, and excellent preservation is obtained. It is clear that sex is obtained. On the other hand, in the control sample to which no preservative was added, or in the comparative sample 2 and the comparative sample 3 using the compound X and phenol as the preservative, the photographic performance of the obtained light-sensitive material was adversely affected, and the comparative sample 3 was dispersed. The storability of the liquid was inferior.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Sumiko Kimura 3-4,8-905 Tsutsujigaoka, Akishima-shi, Tokyo (56) References JP-A-60-119547 (JP, A) JP-A-53-118527 (JP, A)

Claims (2)

[Claims] 1. A preservative for a photographic colloidal composition, which comprises at least one compound represented by the following general formula as an active ingredient. General formula (However, R ₁ and R ₂ each independently represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms or a hydroxymethyl group, which may be the same or different, and R ₃ represents a hydrogen atom or a carbon atom. It represents a lower alkyl group of 1 to 5.) 2. A photographic colloid composition comprising a photographic colloid composition for coating a constituent layer of a silver halide photographic light-sensitive material, containing at least one compound represented by the following general formula. How to preserve things. General formula (However, R ₁ and R ₂ each independently represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms or a hydroxymethyl group, which may be the same or different, and R ₃ represents a hydrogen atom or a carbon atom. It represents a lower alkyl group of 1 to 5.)