JPS60119547A - Antiseptic method for photographic colloid composition - Google Patents

Abstract

PURPOSE:To prevent degradation and putrefaction due to growth of bacteria, mold, etc. during storage for a long term without adversely affecting other photographic characteristics, by incorporating a specific compd. in the colloid compsn. of a silver halide photosensitive material. CONSTITUTION:A silver halide emulsion layer or an interlayer, etc., contg. colloid, such as gelatin, contains a compd. represented by the formula shown here in which R1 is H, lower alkyl, or CH2OH, and R2 is H or lower alkyl. As a result, degradation and putrefaction of the colloid compsn. due to microorganisms is prevented, and long term storage stability is enhanced without adversely affecting any photographic characteristics, such as sensitivity and fog resistance, and an amt. of antiseptic agent and mold inhibitor to be used can be reduced as compared with the conventional ones, and the use of a combination of this compd. and the conventional one can reduce the consumption of the conventional one.

Description

Detailed Description of the Invention (1) Background Technical Field of the Invention The present invention relates to a method for preserving a photographic colloid composition used in a silver halide photographic light-sensitive material (hereinafter abbreviated as "photosensitive material").

Prior art and its problems A light-sensitive material consists of IIQ, at least one light-sensitive emulsion layer on a support, and optionally a subbing layer, an intermediate layer, a filter layer, an anti-halation layer, a protective layer, and a backing. It is formed by laminating and coating constituent layers such as layers.

These constituent layers may contain silver halide, silver halide,
Contains couplers, masking couplers, stabilizers, inhibitors, filter dyes, antihalation 1F dyes, sensitizing dyes, colloidal silver, ultraviolet absorbers, anti-IL agents, matting agents, surfactants, etc.

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

Here, the term "wood-philic colloid" refers to a polymeric substance used to prevent the aggregation of silver halide, colloidal silver, and other additives, and gelatin is the most widely used, while albumin, agar, gum arabic, etc. natural substances such as acylated gelatin, phthalated gelatin, hydroxyethylcellulose, and highly water-soluble polymers such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, and polyvinylpyrrolidone. Molecules etc. are used.

The above-mentioned constituent layer additive solution and constituent layer coating composition are susceptible to the propagation of microorganisms such as bacteria and mold during storage, and deteriorate or spoil when stored for a long period of time. This leads to adverse photographic effects due to a decrease in the viscosity of the coating composition, a decrease in the physical strength of the surface film of the photosensitive material, and metabolites of the grown microorganisms, resulting in a serious defect.

In order to prevent defects caused by such microorganisms, it is known to add bactericides and fungicides to coating compositions.

For example, aromas such as phenol, thymol, trichlorophenol, cresol, p-chloro-I-cresol, 0-phenylphenol, chlorophene, 3,4.5-)ribromosalicylanilide, 4-n-hexylresocyl, etc. Group phenols; Compounds having a car-nyl group such as formaldehyde, paraformaldehyde, geltaraldehyde, and methylolchloraldehyde; Carboxylic acids or their esters such as benzoic acid, p-oxybenzoic acid ester, and sorbic acid; 2-mercaptobenzo Nitrogen-containing heterocyclic compounds such as thiazole and 2-(4-thiazolyl)-benzimidazole; Mercury compounds such as phenylmercury and mercuric phenylpropionate; Antibiotics such as neomycin and kanamycin; generally used as bactericidal or fungicidal agents. Some of them are also known to be used for photography.

However, these substances are not effective against hydrophilic colloids unless they are added to the soybean paste, or they are harmful to living organisms or photographically harmful, so they are not satisfactory. do not have.

For example, phenols do not exhibit a preservative effect unless they are added in an amount of 2% or more of the hydrophilic colloid.

Formaldehyde and the like tend to cause fog on photosensitive materials.

Benzthiazoles and the like tend to have a desensitizing effect.

Mercury compounds are harmful to living organisms and cannot be used.

Furthermore, the benzisothiazolone described in JP-A No. 54-27424 tends to cause fogging, and
Neomycin described in No. 81 is expensive.

As described above, none of the conventional bactericidal agents or antifungal agents exhibits satisfactory properties in practical use when added to photographic colloid compositions.

II. OBJECTS OF THE INVENTION The first object of the present invention is to effectively protect additive solutions and coating composition solutions for the constituent layers of photosensitive materials from microorganisms, improve their storage stability, and use bactericidal or antifungal agents. It is an object of the present invention to provide a method that requires only a small amount of usage.

The second]] target is the photographic performance of the light-sensitive material (sensitivity, fog,
An object of the present invention is to provide a method for preserving a coating composition that does not have any adverse effect on storage stability, etc.

Other objects of the invention will become apparent from the description below.

(2) It has been found that one of the objects of the present invention can be achieved by incorporating at least one compound represented by the following general formula into a specific composition of the invention.

(]] In the general formula 2, R1 represents hydrogen, a lower alkyl group or a hydroxymethyl group, and R2 represents hydrogen or a lower alkyl group.) In the above general formula, R1 is hydrogen, a lower alkyl group,
The hydroxymethyl group and R2 represent hydrogen or a lower alkyl group, and the lower alkyl group has 1 to 5 carbon atoms.
, especially preferred.

The compounds of the present invention represented by the above general formula are particularly useful for storing capping agent dispersions, coupler dispersions, silver halide emulsions, etc., or coating compositions containing mixtures thereof.

The amount of the compound of the present invention to be used is determined by the W to be added in an aqueous solution, etc.
The range of o,ooi to 0.05% by weight is preferable.

However, it goes without saying that this range may be increased or decreased depending on the type of photosensitive material, type of aqueous solution, storage conditions, etc.

The compounds of the present invention can be used in water or methanol, ethanol,
Improper tool may be dissolved in a solvent such as acetone, ethylene glycol, or a mixed solvent thereof and added as a solution, or it may be dissolved in a high boiling point solvent or a low point solvent and then emulsified and dispersed using a surfactant. However, it may be added.

Specific examples of the compounds of the present invention are shown below.

Blue 02 Zan H3 These compounds can be synthesized with reference to the following literature, and some are commercially available from San-Ai Oil Co., Ltd.

(+) Henry, Recueil des tr
avaux chimiquesdes Rays-B
as, IS 251(2) Maas, Chemis
chess Zentralblatt, 18991 1
79 (3) E, 5chIIlidt, Berichte
der DeutchenChemischen G
e5ellschaft, 52 397(4) E,
Schmidt, 1bid, 55 317(5) H
Enry, Chemiehes Zentralbla
tt, 18E17II 33B In this case, in particular, the synthesis of compound (1) can be carried out according to documents (1), (2) or 3.
) Compound (2) should be synthesized according to Reference (2), Compound (3) should be synthesized according to Reference (5), and Compound (4) should be synthesized according to Reference 1 (2).

Note that the timing of addition of the compound of the present invention is arbitrary depending on the time point at which the antiseptic effect is expressed.

Such photographic colloid compositions to which the compounds of the present invention are added are solutions of hydrophilic colloids in aqueous solvents.

The wood-philic colloid and aqueous solvent used are as described above.

The additive contained in the photographic colloid composition that is the object of the present invention may be any of the usual photographic additives. One particularly preferred example is shown below.

i) Coupler: α-(4-carboxyphenoxy)-α-pivalyl 2
-chloro5-(y-2,4-di-tert-amylphenoxy)butyramide]acetanilide α-piparyl-2-chloro5-[γ-2.4-di-t
ert-amylphenoxy]butyramide]acetanilide α-benzoyl-2-chloro-5-[α-dodecyloxycarbonyl)ethoxycarbonyl]acetanilide α-(4-carboxyphenoxy)-α-piparyl 2
-chloro5-[α-3-pentadecylphenoxy)butyramide]acetanilide 1-(2,4,8-)dichlorophenyl)-3-(3-(2,4-di-tert
-amylphenoxyacetamide)penzamide]-5
-Pyrazolone 1-(2,4,8-)dichlorophenyl)-3-(3-
dodecylsuccinimidobenzamide)-5-pyrazolone4.4'-methylenebis(1-(2,4,fl-)dichlorophenyl)-3-(3-(2,4-di-tert-
amylphenoxyacetamide)benzamide]-5-
pyrazolone) 1-(2,4,6-trichlorophenyl)-3-(2-
Rolow 5-octadecylsuccinimide anilino)-5
-Pyrazolone 1-(2,4,8-)dichlorophenyl)-3-(2-
Chloro-5-tetradecanamide anilino)-5-pyrazolone l-hydroxy-N-(8-(2,4-di-tert-
amylphenoxy)butyl-2-naphthamide 2.4
-dichloro-3-butyl-6-(2,4-di-tcrt
-amylphenoxyacetamito)phenol 1-hydroxy-4-(4-nitrophenylcarbamoyl)oxy-N-(8-(2,4-di-tert-amylphenoxy)butyl-2-naphthamide, etc.).

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

1ii) Noble metal sensitizers: chloroauric acid, potassium chlorooleite, potassium aurithiocyanate, ammonium chloroparadate, sodium chloride resort, etc.

ii) Wi yellow sensitizers: activated gelatin, sodium thiosulfate, ammonium thiosulfate, N-7 lyrhodanine, etc.

■) Reduction sensitizers: stannous chloride, tetraethylenetriamine, iminoaminomethanesulfinic acid, etc.

i) Sensitizing dye: Anhydro-8-ethyl-bis(3-sulfopropyl-
5-chloro)-oxacarpocyanine hydroxyte, anhydro-8-ethyl-bis(3-sulfobutyl-5
-chloro)-thiacarbocyanine hydroxide.

3-sulfobutyl-3'-ethylthiacyanine sodium salt, etc.

ii) Stabilizer: 4-hydroxy-6-methyl-1,3,3a,? - Tetrazaindene benzothiazole, etc.

1ii) Matting agents Nisilica, magnesium phosphate, titanium oxide, polymethyl methacrylate, polystyrene, starch, cellulose acetate propionate, etc.

11L) Surfactant: Saponin, polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene lauryl ether VL
W1 soda, polyoxyethylene nonylphenyl ether, polyoxyethylene-polyglycidal block copolymer, etc.

! 1) Polymer wood-philic colloids: Copolymers of methyl methacrylate, n-butyl acrylate-1, butadiene, styrene, vinyl acetate, vinyl chloride, etc.

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

■Specific effects of the invention According to the invention, one of the compounds represented by the above general formula is added to a photographic colloid composition used for coating photosensitive materials.
2, the photographic colloid composition can be effectively protected from microorganisms.

That is, the storage stability is significantly improved compared to when conventional bactericides or fungicides are used.

Furthermore, the amount used can be reduced compared to conventional products.

Furthermore, the photographic performance of the light-sensitive material, such as sensitivity, fog, etc.
There is no adverse effect on storage stability, etc.

Furthermore, since it is harmless to living organisms, it is safe for manufacturers and users of photosensitive materials.

Furthermore, since it is inexpensive, it does not increase the cost of photosensitive materials unlike antibiotics.

Therefore, it is possible to significantly reduce the burden on equipment such as storage equipment, constraints on production planning, failures in photographic performance and physical properties, etc. compared to conventional methods, and improve productivity and quality reliability. , which has an extremely large effect.

(2) Specific Examples of the Invention The present invention will now be described in more detail according to specific examples.

Example 1 25 mg of the compounds (1) and (2) of the present invention and phenol and benzinthiazolone as comparative compounds were added to one aqueous dispersion of polymethyl methacrylate agent having an average particle size of 3 Bm.
A strain of the genus Pseudomonas was added to the mixture, and the mixture was left at 25°C for one week, and the number of bacteria and the state of dispersion of the matting agent were observed.

Further, using these samples, high-sensitivity X-ray photosensitive materials (Samples Nos. 1 to 5) were manufactured by the following method.

That is, a high-sensitivity X-rayobromide silver emulsion and a protective layer consisting of the following composition were simultaneously coated on a polyethylene terephthalate support.

Gelatin 50g Sodium diisooctylsulfosuccinate 3oIII ・：i? Electric protection 11 2 agents 2g 30 g of the above matting agent dispersion Added water to make it one sentence.

Sensitometry was performed on these samples under the following conditions.

For sensitometry, the sample was exposed using a KS-1 sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), developed with the following developer (40°C for 30 seconds), fixed, washed with water, and dried.

[Developer composition]

Anhydrous sodium sulfite 70g Hydroquinone log Charcoal butyric acid l)f, salt 20g 1-phenyl-3-pyranurone 0.35g Suichu Northern Lium 5g 5-methylbenzotriazole 0,05g Potassium bromide 5g Glutaraldehyde bisulfite 132 15 g glacial acetic acid
Add 8g water to make one sentence.

The results are shown in Table 1.

As is clear from Table 1, sample No. 3 according to the present invention.
It can be seen that Sample No. 4 has no adverse effect on photographic performance, effectively suppresses the number of cutillia, and does not cause aggregation of the matting agent even after storage for one week.

Example 2 To a color magenta coupler dispersion, a UV absorber dispersion, and a green-sensitive silver iodobromide emulsion, 25 mg of the compound of the present invention and phenol as a comparative compound were added in one sentence.

A strain of Pseudomonas was added to the coupler dispersion, and Er+trobacterium was added to the UV absorber dispersion.
1 strain of the genus r, and Ac1 for the green-sensitive silver iodobromide emulsion.
One strain of netobacter genus was inoculated, and two
The samples were left at 5°C for one week, a storage test was performed, and the number of bacteria was measured.

In addition, as a 1 magenta coupler, 1-(2,4,6-)lichloro)phenyl-3-(3-
(2,4-di-tert-amylphenoxy)acetamide]benzamide 5-pyrazolone.

As a UV absorber, was used.

In addition, as green-sensitive silver iodobromide, the average particle size is 1 gm, 5
A high-sensitivity layer made of tetradecahedral silver iodobromide containing mol % of silver iodide, and an il containing 7 mol % of silver iodide with an average grain size of 4 km.
Type I silver iodobromide was used in the low speed layer.

Using the above sample, a highly sensitive multilayer color negative photographic material as described below was manufactured.

That is, the following layers were sequentially coated on a triacetate film support.

1st layer: antihalation layer containing black colloidal silver (
(Dry film thickness: 1 μm) Second layer: Gelatin intermediate layer containing 2,5-di-tert-octylhydroquinone (Dry film thickness: t gll ) Third layer: Red-sensitive emulsion layer containing 1-hydroxy as a cyan coupler per mole of silver halide. -N-(y-(2,4-tert-
Amylphenoxy)-butyl)-2-naphthamide6.
8X10-2 mol, 1-hydroxy-N-(8-(2,4-di-tert-
amylphenogysi)-butyl)-4,-(2-ethoxycarbonylphenylazo)-2-naphthamide 1.5X
10-2 mol and 2-(1-phenyl-5-tetrazolylthio)-4-( as development inhibitor releasing material)
Red-sensitive silver iodobromide emulsion layer containing 4X10-3 moles of 2,4-di-tert-acylphenoxyacetamide)-1-indanone (silver iodobromide emulsion containing 8 mol% silver bromide, dry film thickness 6 μf)
f1) 4th layer: Intermediate layer Same as the 2nd layer.
-(2,4-di-tert-amylphenoxy)acetamide]benzamide 5-pyrazolone 6.0XIO-
1-(2,4,8-)lichloro)phenyl-3-(3
-(octadecenyl succinimide)-2-chloro]
AniliF-4-(γ-naphthylazo)-5-pyrazolone 1.4X10-' mol and 2-(1-phenyl-5-tetrazolylthio)-4-( as development inhibitor releasing material)
Green-sensitive silver iodobromide emulsion layer containing 4X10-3 moles of 2,4-di-tert-amylphenoxyacetamide)-1-indanone (dry film thickness 3.5 gm): Jj6 layer: green layer green-sensitive high-sensitivity emulsion The same compounds as the magenta coupler, colored coupler and development inhibitor releasing substance of the layer are respectively 1, OX I O-2 mo, uz per mole of silver halide.
, 5X I 0-3-t-l, 1 .

Green-sensitive high-sensitivity emulsion layer containing 5 X I O-3 mol (dry film thickness 2,5 p, m) 7th layer: intermediate layer Same as 2nd layer 8th layer: yellow filter layer yellow colloidal silver and 2. Gelatin layer containing 5-di-tert-octylhydroquinone (dry film thickness: 1.2 mm) 9th layer: Blue-sensitive emulsion layer containing α-piparoyl-α-(1-benzyl-2) as a yellow coupler per mole of silver halide. ,4-dioxyimidazolidine)-3-yl-2'-chloro-5-[
γ-(2,4-di-tert~amylphenoxy)butyramide]acetanilide 2.5X10-1 mol ω-Bromo-ω-(1-phenyl-5-tetrazolylthio)-4-lauroylamide acetophenone as development inhibitor releasing substance 5 X
Blue-sensitive silver iodobromide emulsion layer containing 10 −3 mol % of silver iodide (silver iodobromide emulsion dry film thickness 7 tiles II containing 6 mol % of silver iodide) 10th layer: protective layer dispersion liquid as a UV absorber, and a gelatin layer containing polymethyl methacrylate as a matting agent (dry film thickness 1 #Lm).
For the sixth layer and the first θ layer, a coupler dispersion, a UV absorber dispersion, and a green-sensitive silver iodobromide emulsion, which had been subjected to the above-mentioned storage stability test (deterioration due to decay), were used.

These samples 1 (No. 7 to 11) were subjected to wedge exposure through a green filter, and then subjected to the following development process.

On the other hand, after coating and drying, the samples were stored for 3 months at 25°C and relative humidity of 60%, and sensitometry was carried out in the same way. Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water Washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds The composition of the treatment liquid used in each treatment step was as follows.

[Color developer composition]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine sulfuric acid 1'11.2.0 g Potassium charcoal 37.5 g Sodium bromide 1.3 g Trisodium nitrilotriacetic acid salt l water 1n2, 5 g Potassium hydroxide 1.0 g Add water to make 11 and adjust p)I to 10.0.

[Bleach solution composition]

Iron ethylenediaminetetraacetate Ammonium salt 100.0g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0 g Ammonium bromide 150.0g Glacial acetic acid 10.0 Add water to make one part and adjust pH to 6.0.

[Fixer composition]

Ammonium thiosulfate 50% water solution method 160 ■ Interchange Anhydrous sodium sulfite 32g Add water to 12 and adjust pH to 6.5.

[Stable bath composition]

Formalin 37% aqueous solution 5. O m sentence conitax [
[manufactured by Konishiroku Photo Industry Co., Ltd.] Add 7.5 ta of water to make it stand.

Table 2 shows the number of bacteria in the colloid composition and the sensitometric results. In addition, the sensitivity is the same as when the sample falls. The relative sensitivity is shown with the sensitivity of 7 being 100.

As is clear from Table 2, between the samples according to the present invention, 9
, 10 had no adverse effect on photographic performance and showed a strong inhibitory effect on bacterial growth.

- sample without disinfectant, 8), and sample containing phenol as a comparative compound, sample 11, were rotten by bacteria, resulting in decreased sensitivity and Dwin's upper arm.

Applicant: Konishiroku Photography Co., Ltd. Applicant: San-Ai Oil Co., Ltd. Agent Patent Attorney Yo Ishii -

Claims (1)

[Claims] (1) A photographic colloid composition characterized in that the photographic colloid composition used for coating the constituent layers of a silver halide photographic light-sensitive material contains at least one compound represented by the following general formula. Preservation method. (In the above general formula, R1 represents hydrogen, lower alkyl J, (or hydroxymethyl group, and R2 represents hydrogen or lower alkyl group.)